Height independent compressive modulus of vertically aligned carbon nanotube arrays

The compressive modulus of dense vertically aligned multiwalled carbon nanotube (CNT) arrays synthesized by chemical vapor deposition was investigated using an optically probed precision-loading platform. For CNT arrays with heights ranging from 15 to 500 microm, the moduli were measured to be about 0.25 MPa and were found to be independent of array height. A continuum mechanics model based on multimode buckling guided by the wavy features of CNT arrays is derived and explains well the measured compressive properties. The measured compressive modulus of the CNT arrays also satisfies the "Dahlquist tack criterion" for pressure sensitive adhesives, which was previously observed for these vertically aligned CNT arrays (Zhao, Y., et al. J. Vac. Sci. Technol., B 2006, 24, 331-335).     

Ultrahigh density modulation of aligned single-walled carbon nanotube arrays

Controlling the densities of aligned single-walled carbon nanotube arrays (SWNTs) on ST-cut quartz is a critical step in various applications of these materials. However the growth mechanism for tuning SWNT density using the chemical vapor deposition (CVD) method is still not well understood, preventing the development of efficient ways to obtain the desired results. Here we report a general “periodic” approach that achieves ultrahigh density modulation of SWNT arrays on ST-cut quartz substrates—with densities increased by up to ∼60 times compared with conventional methods using the same catalyst densities—by varying the CH₄ gas “off” time. This approach is applicable to a wide range of initial catalyst densities, substrates, catalyst types and growth conditions. We propose a general mechanism for the catalyst size-dependent nucleation of SWNTs associated with different free carbon concentrations, which explains all the observations. Moreover, the validity of the model is supported by systematic experiments involving the variation of key parameters in the “periodic” CVD approach.      

Control of neuronal network organization by chemical surface functionalization of multi-walled carbon nanotube arrays

Carbon nanotube substrates are promising candidates for biological applications and devices. Interfacing of these carbon nanotubes with neurons can be controlled by chemical modifications. In this study, we investigated how chemical surface functionalization of multi-walled carbon nanotube arrays (MWNT-A) influences neuronal adhesion and network organization. Functionalization of MWNT-A dramatically modifies the length of neurite fascicles, cluster inter-connection success rate, and the percentage of neurites that escape from the clusters. We propose that chemical functionalization represents a method of choice for developing applications in which neuronal patterning on MWNT-A substrates is required.     

Enhanced Electrical Properties in Carbon Nanotube/Poly （3-hexylthiophene） Nanocomposites Formed Through Non-Covalent Functionalization

Poly(3-hexylthiophene) (P3HT) has received much attention as a good candidate to replace inorganic semiconductors for flexible electronics due to its solution-processability. However, the low charge mobility of P3HT is an obstacle to its commercialization. To overcome this problem, we propose a new non-covalent functionalization method for carbon nanotubes (CNTs) for use in CNT/P3HT nanocomposites. By using modified pyrene molecules with hydrophobic long alkyl chains, the non-covalently functionalized CNTs can become well dispersed in hydrophobic solutions and organic semiconductor matrices. Fabrication of organic thin-film transistors (OTFTs) from the non-covalently functionalized CNT/organic semiconductor nanocomposites shows that our non-covalent functionalization method significantly reduces damage to CNTs during functionalization when compared with covalent functionalization by treatment with acids. The OTFTs show 15 times enhancement of field effect mobility (1.5 × 10⁻² cm²/(V·s)) compared to the mobility of OTFTs made from pure P3HT. This enhancement is achieved by addition of only 0.25 wt% of CNTs to P3HT.      

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。     

Efficient surface functionalization of vertically-aligned carbon nanotube arrays using an atmospheric pressure plasma jet system

We demonstrate the facile and efficient surface functionalization of vertically-aligned carbon nanotube (VCNT) arrays using an atmospheric pressure plasma jet (APPJ) system. The VCNT arrays were synthesized on Fe-deposited SiO₂ wafers using an acetylene carbon source by thermal chemical vapor deposition method. To functionalize the surface of the VCNT arrays, the APPJ system was ignited using nitrogen gas at high voltage of 15 kV and frequency of 25 kHz. We varied the treatment time of the APPJ and the inter-distance between plasma jet and top surface of the VCNT in order to systematically investigate the optimal conditions of the APPJ system. The hydrophobic nature of the as-grown VCNT arrays was drastically changed to hydrophilic character via the facile APPJ treatment. X-ray photoelectron spectroscopy confirmed the formation of hydrophilic functional groups such as hydroxyl and carboxyl groups, and nitrogen-doping-related functionalities such as amines, in addition to pyrrolic- and pyridinic-bonding. The results prove that the APPJ treatment is a facile and efficient method for the surface modification of nanomaterials.     

Effect of compressive strain on electric resistance of multi-wall carbon nanotube networks

The network of entangled multi-wall carbon nanotubes is shown as a conductor whose resistance is sensitive to compressive strain, both in the course of strain growth and when loading/unloading cycles are imposed. If the compression is applied, the resistance decrease is up to 25% at the maximum applied deformation. The experimental data are analysed using the Weibull distribution model and a contact network model to get an estimate of the contact resistance between carbon nanotubes and the formation of contacts in the course of compression.     

Harmonic oscillators of carbon nanotube arrays

The harmonic properties of single-walled carbon nanotube (10, 10) arrays in cantilever geometry of lengths, L = 1,000 to 10,000 nm and diameters, D = 15 to 70 nm have been measured recently, and a linear relationship between the first natural frequency and the ratio of array diameter and the square of the span length, D/L2 was postulated. In the present work the authors show that this relationship is highly nonlinear, especially for large values of the ratio, D/L2. In addition, for a given array length, L = 1000 nm, the first natural frequency of the cantilever is shown to vary little with diameters more than 30 nm and to become asymptotic to a value of 22 MHz as it is further increased. The present study is based on earlier work of the authors wherein the flexural stiffness of the single-walled carbon nanotube (CNT) array of hexagonal symmetry and of non-covalent bonding, due to van der Waals interactions, was predicted in terms of the chirality of the nanotubes and the shearing transfer efficiency between nanotubes when subjected to flexural deformation. In addition, predictions are shown to be in agreement with the experimental evidence wherein the flexural modulus of the CNT array decreases with an increase in array diameter.     

Nitrogen-doped carbon nanotube arrays grown on graphene substrate

Nitrogen-doped carbon nanotube (N-doped CNT) arrays have been synthesized on graphene substrate by chemical vapor deposition process, in which iron nanoparticles (NPs) assembled on the graphene sheet were generated in situ from the reduction of Fe₃O₄ NPs/reduced graphene oxide (RGO) and were used as catalyst. The morphology and structure of the N-doped CNT arrays were investigated by field emission scanning electron microscope and high-resolution transmission electron microscope. The N-doped CNTs were bamboo-shaped and the density can be controlled by modulating the density of catalyst NPs on RGO sheets. The concentration and incorporation of nitrogen were studied by elemental analysis, X-ray photoelectron spectroscope and Raman analysis, and the results showed that the nitrogen content was around 3 wt.%. Because of the good conductivity of graphene structure, N-doped CNT arrays grown on graphene substrate may be promising candidates as noble metal-free electrodes for oxygen reduction reaction in the future.     

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.     

Study on the controllable scale-up growth of vertically-aligned carbon nanotube arrays

Vertically aligned carbon nanotubes (VA-CNTs) with high purity have been grown on quartz substrate via the gas phase catalytic chemical vapour deposition (CVD) by using ferrocene as the catalyst source and camphor as the carbon source. The effects of catalyst concentration, flow rate and water assistance on the morphology and structure of VA-CNTs are investigated by SEM, TEM, Raman and XPS characterizations. Under the optimized CVD conditions with modest ferrocene concentration and flow rate, dense and well VA-CNT arrays have been obtained. The water concentration should be controlled to improve CNTs alignment and impurity without damaging the walls of CNTs.     

Efficient fabrication of carbon nanotube micro tip arrays by tailoring cross-stacked carbon nanotube sheets

Carbon nanotube (CNT) micro tip arrays with hairpin structures on patterned silicon wafers were efficiently fabricated by tailoring the cross-stacked CNT sheet with laser. A blade-like structure was formed at the laser-cut edges of the CNT sheet. CNT field emitters, pulled out from the end of the hairpin by an adhesive tape, can provide 150 μA intrinsic emission currents with low beam noise. The nice field emission is ascribed to the Joule-heating-induced desorption of the emitter surface by the hairpin structure, the high temperature annealing effect, and the surface morphology. The CNT emitters with hairpin structures will greatly promote the applications of CNTs in vacuum electronic devices and hold the promises to be used as the hot tips for thermochemical nanolithography. More CNT-based structures and devices can be fabricated on a large scale by this versatile method.     

Degradation and failure of field emitting carbon nanotube arrays

It has been observed experimentally that the collective field emission from an array of Carbon Nanotubes (CNTs) exhibits fluctuation and degradation, and produces thermal spikes, resulting in electro-mechanical fatigue and failure of CNTs. Based on a new coupled multiphysics model incorporating the electron-phonon transport and thermo-electrically activated breakdown, a novel method for estimating accurately the lifetime of CNT arrays has been developed in this paper. The main results are discussed for CNT arrays during the field emission process. It is shown that the time-to-failure of CNT arrays increases with the decrease in the angle of tip orientation. This observation has important ramifications for such areas as biomedical X-ray devices using patterned films of CNTs.     

Electrochemical characterization of parylene-embedded carbon nanotube nanoelectrode arrays

A novel parylene-embedded carbon nanotube nanoelectrode array is presented for use as an electrochemical detector working electrode material. The fabrication process is compatible with standard microfluidic and other MEMS processing without requiring chemical mechanical polishing. Electrochemical studies of the nanoelectrodes showed that they perform comparably to platinum. Electrochemical pretreatment for short periods of time was found to further improve performance as measured by cathodic and anodic peak separation of K(3)Fe(CN)(6). A lower detection limit below 0.1?μM was measured and with further fabrication improvements detection limits between 100?pM and 10?nM are possible. This makes the nanoelectrode arrays particularly suitable for trace electrochemical analysis.     

The growth of freestanding single carbon nanotube arrays

Regular arrays of freestanding single carbon nanotubes (CNTs) were prepared on Ni dot arrays by dc plasma-enhanced chemical vapour deposition. The size of the Ni dot was reduced for single CNT growth by means of conventional photolithography and a lateral wet-etch process. The vertical alignment of a single CNT was directly dependent on the location of the catalyst metals. Using this method, well-separated and well-defined regular arrays of freestanding CNTs can be fabricated and the process can be scaled up at a lower cost than electron beam lithography, which is encouraging for applications in field emitters and nanoelectrodes.     

Growth of ZnO nanowires on modified well-aligned carbon nanotube arrays

Single-crystal ZnO nanowires were successfully grown on modified well-aligned carbon nanotube (CNT) arrays by a hydrothermal process. The pre-deposited ZnO grains on the CNTs served as the nucleation sites for the growth of ZnO nanowires. The attached growth of ZnO nanowires on the well-aligned CNT arrays formed a 3D configuration. The 3D hybrid nanostructured material could find application in sensors and other electronic or optoelectronic devices.     

Growth of single-walled carbon nanotube arrays from samarium on substrates

In this letter, it is reported for the first time that samarium is an effective catalyst for single-walled carbon nanotubes(SWNTs) growth via a chemical vapor deposition(CVD) process. Horizontally superlong well-oriented SWNT arrays can be generated under suitable conditions by using ethanol as carbon source. The single-wall structure was characterized by scanning electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from samarium have better conductivity and better structural uniformity with less defects. This rare earth metal element provides not only an alternative catalyst for SWNTs growth but also a possible way to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.     

TiO2纳米管阵列膜对牛血清白蛋白的吸附与脱附

采用电化学阳极氧化法以含氟的乙二醇溶液为电解液阳极氧化纯钛制备出排列规则的高长径比TiO2纳米管阵列膜,并用扫描电镜(SEM)、比表面积仪表征了TiO2纳米管阵列膜的形貌和比表面积。结果表明,所制得的TiO2纳米管阵列的管径约180nm,管长可达230μm,比表面积约59.8m2/g。以牛血清白蛋白(BSA)为药物蛋白分子的模型,并研究了TiO2纳米管阵列膜对BSA的吸附和脱附行为,考察了溶液pH值、BSA初始浓度和溶液离子强度对BSA吸附的影响与吸附态的BSA在不同pH值的PBS溶液中的释放行为。结果表明,BSA分子在其等电点(pH值=4.8)附近较容易吸附到TiO2纳米管上,吸附量随着BSA初始浓度的增加而增加,较高的离子强度会降低BSA的吸附,碱性条件下吸附态的BSA容易从TiO2纳米管上脱附,并由于纳米管的扩散限制效益呈现一定程度的缓释。     

Effect of defect and C60s density variation on tensile and compressive properties of peapod

The purpose of the current study is to investigate the effect of defects on a single wall carbon nanotube (SWCNT) filled with C60 (peapod). A series of Molecular Dynamics simulation are carried out to investigate the compressive and tensile properties of the CNTs and peapods. The paper presents the effect of the two common crystallography defects (Stone–Wales defect and vacancy defect) on mechanical properties of the peapod. The tension and compression of the defective peapod is determined and is compared with an empty SWCNT. It is shown that encapsulating the C60s into the nanotubes under compression enhances the compressive strength of the structure. However, it does not have a favorable influence on the tensile strength of nanotubes. It is seen that defects weaken compressive and tensile strength of peapods. The effects of different defects on compressive properties of peapods do not much differ from each other. On the other hand, the type of defect is a dominant factor for nanotubes under tension.