Substrate morphology induced self-organization into carbon nanotube arrays, ropes, and agglomerates

In this paper, hydrophobic carbon nanotube (CNT) arrays, ropes, and agglomerates were synthesized through self-organization on quartz substrates with different micro-structures under the same growth condition. On a flat substrate, a uniform woven structure was formed which resulted in a synchronous growth into an array. When the substrate with 10?μm round concaves distributed on the surface was adopted, the woven structure was sporadic and a CNT cluster was grown in the concave. With further growth, CNT ropes were self-organized. Subsequently, when the substrate consisting of irregular ～100?nm gaps was used, the initial woven structure was high density, thus resulting in the formation of CNT agglomerates. Study results showed that CNT arrays grown on the flat substrate were of the highest purity and had a contact angle of 153.8 ± 0.9°. Thus, the self-organization behavior among CNTs was in situ modulated by different substrate morphology without further treatments. This provides us with an additional understanding of the self-organization of CNTs during growth, as well as strategies for the controllable synthesis of CNTs with fixed properties.     

Linear increases in carbon nanotube density through multiple transfer technique

We present a technique to increase carbon nanotube (CNT) density beyond the as-grown CNT density. We perform multiple transfers, whereby we transfer CNTs from several growth wafers onto the same target surface, thereby linearly increasing CNT density on the target substrate. This process, called transfer of nanotubes through multiple sacrificial layers, is highly scalable, and we demonstrate linear CNT density scaling up to 5 transfers. We also demonstrate that this linear CNT density increase results in an ideal linear increase in drain-source currents of carbon nanotube field effect transistors (CNFETs). Experimental results demonstrate that CNT density can be improved from 2 to 8 CNTs/μm, accompanied by an increase in drain-source CNFET current from 4.3 to 17.4 μA/μm.     

Drying induced upright sliding and reorganization of carbon nanotube arrays

Driven by capillary force, wet carbon nanotube (CNT) arrays have been found to reorganize into cellular structures upon drying. During the reorganization process, individual CNTs are firmly attached to the substrate and have to lie down on the substrate at cell bottoms, forming closed cells. Here we demonstrate that by modifying catalyst structures, the adhesion of CNTs to the substrate can be weakened. Upon drying such CNT arrays, CNTs may slide away from their original sites on the surface and self-assemble into cellular patterns with bottoms open. It is also found that the sliding distance of CNTs increases with array height, and drying millimetre tall arrays leads to the sliding of CNTs over a few hundred micrometres and the eventual self-assembly into discrete islands. By introducing regular vacancies in CNT arrays, CNTs may be manipulated into different patterns.     

X-ray images obtained from cold cathodes using carbon nanotubes coated with gallium-doped zinc oxide thin films

X-ray imaging data obtained from cold cathodes using gallium-doped zinc oxide (GZO)-coated CNT emitters are presented. Multi-walled CNTs were directly grown on conical-type (250 μm-diameter) tungsten-tip substrates at 700 °C via inductively coupled plasma-chemical vapor deposition (ICP-CVD). GZO films were deposited on the grown CNTs at room temperature using a pulsed laser deposition (PLD) technique. Field-emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) were used to monitor the variations in the morphology and microstructure of the CNTs before and after GZO coating. The formation of the GZO layers on the CNTs was confirmed using energy-dispersive X-ray spectroscopy (EDX). The CNT-emitter that was coated with a 10-nm-thick GZO film displayed an excellent performance, such as a maximum emission current of 258 μA (at an applied field of 4 V/μm) and a threshold field of 2.20 V/μm (at an emission current of 1.0 μA). The electric-field emission characteristics of the GZO-coated CNT emitter and of the pristine (i.e., non-coated) CNT emitter were compared, and the images from an X-ray system were obtained by using the GZO-coated CNT emitter as the cold cathode for X-ray generation.     

Super-long aligned TiO2/carbon nanotube arrays

5?mm long aligned titanium oxide/carbon nanotube (TiO(2)/CNT) coaxial nanowire arrays have been prepared by electrochemically coating the constituent CNTs with a uniform layer of highly crystalline anatase TiO(2) nanoparticles. While the presence of the TiO(2) coating was confirmed by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and x-ray diffraction, the resultant TiO(2)/CNT coaxial arrays were demonstrated to exhibit minimized recombination of photoinduced electron-hole pairs and fast electron transfer from the long TiO(2)/CNT arrays to external circuits. This, in conjunction with the aligned macrostructure, facilitates the fabrication of TiO(2)/CNT arrays for various device applications, ranging from photodetectors to photocatalytic systems. Thus, the millimeter long TiO(2)/CNT arrays represent a significant advance in the development of new macroscopic photoelectronic nanomaterials attractive for a variety of device applications beyond those demonstrated in this study.     

Direct growth of aligned carbon nanotubes on bulk metals

There are several advantages of growing carbon nanotubes (CNTs) directly on bulk metals, for example in the formation of robust CNT-metal contacts during growth. Usually, aligned CNTs are grown either by using thin catalyst layers predeposited on substrates or through vapour-phase catalyst delivery. The latter method, although flexible, is unsuitable for growing CNTs directly on metallic substrates. Here we report on the growth of aligned multiwalled CNTs on a metallic alloy, Inconel 600 (Inconel), using vapour-phase catalyst delivery. The CNTs are well anchored to the substrate and show excellent electrical contact with it. These CNT-metal structures were then used to fabricate double-layer capacitors and field-emitter devices, which demonstrated improved performance over previously designed CNT structures. Inconel coatings can also be used to grow CNTs on other metallic substrates. This finding overcomes the substrate limitation for nanotube growth which should assist the development of future CNT-related technologies.     

Catalytic-free growth of VACNTs for energy harvesting

Abstract

The present study introduces a process to grow micro-honeycomb (µ-HC) vertically aligned carbon nanotubes (VACNTs) using thermal chemical vapor deposition technique. Methane is used as a source of carbon and hydrogen gas as a reducing agent. Where, the fabricated µ-HC structure reported in literature involves complex synthesis process and requires a catalyst layer, the novelty of the process used here lies in the fact that no catalyst layer is used for the growth of CNT network, rather copper foil is used as a substrate. The in-situ cracking of CNTs due to water treatment leads to the formation of µ-HC CNT network, which is confirmed by Raman spectroscopy. Further scanning electron microscopy analysis shows that the length of developed µ-HC CNT is ～5?µm. Hexagonal µ-HC network shows more than 94% absorption in UV-Vis-NIR wavelength region. The designed process provides high-yield with a low-cost synthesis of vertically aligned CNTs having 3?D microarchitecture. The fabricated CNT network can be used as an electrode for supercapacitor, as an active layer in a photovoltaic cell and most of the energy harvesting devices.     

定向碳纳米管阵列在石英玻璃基底上的模板化生长研究

分别以带有刻痕的石英玻璃和溅射过Au膜的石英玻璃为生长基底,通过催化裂解二茂铁和二甲苯混合物的方法,在基底上制备出了模板化的定向碳纳米管(CNT)阵列,扫描电镜(SEM)和透射电镜(TEM)观察表明:在这两种基底上生长的定向碳纳米管阵列的模板化程度都很高,其中的碳纳米管多为直径在20～50nm的多壁管(MWNT),且具有很好的定向性。本文还分析、对比了基底材料对定向碳纳米管生长的影响,初步探讨了定向碳纳米管模板化生长的形成机制。     

Direct synthesis of ultralong carbon nanotube bundles by spray pyrolysis and investigation of growth mechanism

A mass of ultralong aligned carbon nanotube (CNT) bundles up to about 8?mm in length was synthesized by utilizing the spray pyrolysis of ferrocene/xylene solutions in the absence of promoters, such as thiophene or pure sulfur, and etching agents, such as plasma, oxygen, ethanol or water. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) results indicated the continuous and multi-walled nanotube structure for the CNTs in the macroscopical bundles. A graph demonstrating the correlation between growth time and length of CNT arrays revealed that the maximum growth rate reaches approximately 4612?nm?s(-1). Based on the experimental phenomena and results, a continuous rapid growth mechanism in both directions was proposed, which suggests that longer CNT arrays can be synthesized at this rapid growth rate if the growth time is extended.     

Variable-force microscopy for advanced characterization of horizontally aligned carbon nanotubes

Atomic force microscopy (AFM) performed with variable-force imaging was recently demonstrated to be an accurate method of determining the diameter and number of sidewalls of a carbon nanotube (CNT). This AFM technique provides an alternative to transmission electron microscopy (TEM) when TEM imaging is not possible due to substrate thickness. We have used variable-force AFM to characterize horizontally aligned CNTs grown on ST-cut quartz. Our measurements reveal new aspects of horizontally aligned growth that are essential for enhancing the performance of CNT-based devices as well as understanding the growth mechanism. First, previously reported optimal growth conditions produce a large spread in CNT diameters and a significant fraction of double-walled CNTs. Second, monodispersity is significantly improved when growth temperature is reduced. Third, CNTs with diameters up to 5?nm align to the substrate, suggesting the interaction between CNTs and the quartz lattice is more robust than previously reported.     

Growth of carbon nanotubes on cobalt catalyst film using electron cyclotron resonance chemical vapour deposition without thermal heating

This paper demonstrates that carbon nanotubes (CNTs) can be synthesized on a cobalt coated silicon substrate using electron cyclotron chemical vapour deposition and without intentionally heating the substrate. With the mixed gases of C(3)H(8)/N(2), CNTs with a multi-walled structure and a diameter up to 70?nm have been observed. Results show that the diameter of the CNTs increases with the thickness of the cobalt catalyst film and the amount of nitrogen incorporated in the CNT films considerably influences the structures of the CNTs. Vertically aligned CNTs can be fabricated with a microwave power as low as 300?W and the flow rate ratio of C(3)H(8)/N(2) = 20/20?sccm. The CNTs exhibit a turn-on field of 0.2?V?μm(-1) determined at the emission current density of 10?μA?cm(-2).     

Optimization of field emission properties of carbon nanotubes by Taguchi method

It is the purpose of this study to evaluate the field emission property of carbon nanotubes (CNTs) prepared by microwave plasma-enhanced chemical vapor deposition (MPCVD) method. Nickel layer of 5 nm in thickness on 20-nm thickness titanium nitride film was transformed into discrete islands after hydrogen plasma pretreatment. CNTs were then grown up on Ni-coated areas by MPCVD. Through the practice of Taguchi method, superior CNT films with very low emission onset electric field, about 0.7 V/μm (at J = 10 μA/cm²), are attained without post-deposition treatment. It is found that microwave power has the most important influence on the field emission characteristics of CNT films. The increase of methane flow ratio will downgrade the degree of graphitization of CNT and thus its field emission characteristics. Scanning electron microscope and transmission electron microscopy (TEM) observation and energy dispersive X-ray spectrometer analysis reveal that CNT growth by MPCVD is based on tip-growth mechanism. TEM micrographs validate the hollow, bamboo-like structure of the multi-walled CNTs.     

Aligned carbon nanotube coating on polyethylene surface formed by microwave radiation

Multifunctional carbon nanotube (CNT) architectures have been created on polyethylene (PE) surface by a microwave welding process. The continuous and aligned CNT films drawn from super-aligned CNT arrays can significantly absorb microwave energy and act as a network of nanosized thermal sources to locally melt the PE substrate beneath, leading to polymer wrapping around individual nanotubes. Uniform and highly conductive CNT/PE nanocomposite layer was formed without undermining the original alignment of the CNTs. CNT patterns have also been precisely fabricated on PE samples. The PE/CNT/PE bonds showed high interfacial strengths, which were affected by the duration of microwave radiation. With ultra-low content of CNTs introduced as antistatic agents, the dissipation of surface charges on PE substrate has been tremendously improved.     

Growth and characterization of bamboo-shaped carbon nanotubes using nanocluster-assembled ZnO:Co thin films as catalyst

Bamboo-shaped carbon nanotubes (CNTs) had been successfully fabricated by a plasma enhanced chemical vapor deposition method, in which nanocluster-assembled ZnO:Co thin film was used as catalyst. It was found that bamboo-shaped CNTs were generally grown in a direction perpendicularly to the substrate surface with the tops of CNTs dominated by the droplet-like catalyst covered by the carbon layer. The diameter of CNTs was ranged from 20-50 nm. High resolution of TEM image showed that the typical CNT had a multi-walled structure with an inner core presented. The ordered graphite layers were inclined to an axis of CNT about 18 degrees and the interlayer space of a CNT was about 0.35 nm. Two peaks in Raman spectrum at 1586 cm(-1) and 1372 cm(-1) were identified as G-band and D-band for graphite, respectively. The results showed that catalyst based on ZnO:Co thin films could be used for the growth of CNTs with bamboo-shaped structure.     

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.     

Photolithographic fabrication of gated self-aligned parallel electron beam emitters with a single-stranded carbon nanotube

In this paper we report on the development of a photolithographic process to fabricate a gated-emitter array with single-stranded carbon nanotubes (CNTs) self-aligned to the center of the emitter gate using plasma-enhanced chemical vapor deposition (PECVD). Si tips are formed on a silicon wafer by anisotropic etching of Si using SiO(2) as a mask. Deposition of a SiO(2) insulating layer and Cr-W electrode layers creates protrusions above the Si tips. This wafer is polished, and the Cr-W on the tips is removed. Etching of the SiO(2) using hydrofluoric acid is performed to expose the gated Si tip. Incorporation of a novel diffusion process produces single-stranded CNTs by depositing a thin Ni layer on the Si tips and thermally diffusing the Ni layer to yield a catalyst particle for single-stranded CNT growth. The large surface to volume ratio at the apex of the Si tip allows a Ni particle to remain to act as a catalyst to grow a single-stranded CNT for fabricating the CNT based emitter structure. Diffusion of the Ni is carried out in situ during the heating phase of the PECVD CNT growth process at 600?°C. The diameters of the observed CNTs are on the order of 20?nm. The field emission characteristics of the gated field emitters are evaluated. The measured turn-on voltage of the gated emitter is 5?V.     

Aligned carbon nanotube stacks by water-assisted selective etching

Well-aligned, high-purity carbon nanotube (CNT) stacks of up to 10 layers fabricated in one batch process have been formed by water-assisted selective etching of carbon atoms. Etching takes place at the CNT caps as well as at the interface between CNTs and metal catalyst particles. This simple process generates high-purity CNTs and opens the CNT ends by removing the nanotube caps. High-resolution transmission electron microscopy indicates that the process does not damage CNT wall structures. A mechanism for stacked growth of CNT layers is proposed.     

Growth of long and aligned multi-walled carbon nanotubes on carbon and metal substrates

Well aligned, long and dense multi-walled carbon nanotubes (CNT) can be grown on both carbon fibres and any metal substrates compatible with the CNT synthesis temperature. The injection-CVD process developed involves two stages, including fibre pretreatment by depositing a SiO(2)-based sub-layer from an organometallic precursor followed by CNT growth from toluene/ferrocene precursor mixture. Carbon substrates, as well as metals, can easily be treated with this process, which takes place in the same reactor and does not need any handling in between the two stages. The aligned CNT carpets obtained are similar to the ones grown on reference quartz substrates. The CNT growth rate is fairly high (ca. 30?μm?min(-1)) and it is possible to control CNT length by varying the CNT synthesis duration. The thickness of the SiO(2)-based sub-layer can be varied and is shown to have an influence on the CNT growth. This layer is assumed to play a diffusion barrier layer role between the substrate and the iron based catalyst nanoparticles producing CNT. The CNT anchorage to the carbon fibres has been checked and good overall adhesion proved, which is in favour of a good transfer of electrical charge and heat between the nanotubes and fibre.     

碳纳米管阵列研究进展

在介绍CNT阵列性能的基础上,对国内外直接合成CNT阵列的方法进行了评述,重点阐述了各种方法的基本特点及CNT阵列的生长机理、结构控制和批量制备问题。进而探讨了CNT原生阵列、抽丝形成的CNT丝、以及CNT阵列分散后得到的CNTs在复合材料、力学增强、功能器件等方面的初步应用,展望了CNT阵列的发展趋势,指出低成本、大批量可控制备CNT阵列仍然是未来一段时间内国际研究热点。     

Effect of density variation and non-covalent functionalization on the compressive behavior of carbon nanotube arrays

Arrays of aligned carbon nanotubes (CNTs) have been proposed for different applications, including electrochemical energy storage and shock-absorbing materials. Understanding their mechanical response, in relation to their structural characteristics, is important for tailoring the synthesis method to the different operational conditions of the material. In this paper, we grow vertically aligned CNT arrays using a thermal chemical vapor deposition system, and we study the effects of precursor flow on the structural and mechanical properties of the CNT arrays. We show that the CNT growth process is inhomogeneous along the direction of the precursor flow, resulting in varying bulk density at different points on the growth substrate. We also study the effects of non-covalent functionalization of the CNTs after growth, using surfactant and nanoparticles, to vary the effective bulk density and structural arrangement of the arrays. We find that the stiffness and peak stress of the materials increase approximately linearly with increasing bulk density.