Dual Raman features of double coaxial carbon nanotubes with N-doped and B-doped multiwalls

Double coaxial carbon nanotubes with nitrogen (N)-doped and boron (B)-doped multiwalls possess composite Raman characteristics, originating not only from the outer N-doped but also from inner B-doped layers. Both N and B dopings result in substantial shifts of the characteristic D band and G band of sp(2) carbon constituting nanotube walls but in different ways. The downshift of the G band is correlated with the decreases of electrical resistivity of carbon nanotubes regardless of N or B doping.     

Effects of hydrogen on the formation of aligned carbon nanotubes by chemical vapor deposition

Well-aligned carbon nanotubes with controllable properties were grown on porous silicon substrates by thermal chemical vapor deposition. The morphologies of the carbon nanotubes were varied with the introduction of H2 during the catalyst activation and/or carbon nanotube growth processes. It was found that H2 promotes the growth of carbon nanotubes while preventing the formation of spherical amorphous carbon particles. Without the introduction of H2 during the C2H2 thermal decomposition, aligned carbon nanotubes mixed with spherical carbon particles were formed on the substrate. However, with the introduction of H2, pure carbon nanotubes were synthesized. These nanotubes also had uniform diameters of 10-20 nm, which is much smaller than nanotubes synthesized without H2. The average growth rate of nanotubes was also affected by the introduction of hydrogen into the reaction chamber during nanotube growth. With the addition of hydrogen, the average growth rate changed from 78 nm/s to 145 nm/s. A possible growth mechanism, including the effect of a high ratio of H2 to C2H2, is suggested for the growth of these well-aligned carbon nanotubes with uniform diameters.     

Secondary nanotube growth on aligned carbon nanofibre arrays for superior field emission

We report substantial improvement of the field emission properties from aligned carbon nanotubes grown on aligned carbon nanofibres by a two-stage plasma enhanced chemical vapour deposition (PECVD) process. The threshold field decreased from 15.0 to 3.6 V/microm after the secondary growth. The field enhancement factor increased from 240 to 1480. This technique allows for superior emission of electrons for carbon nanotube/nanofibre arrays grown directly on highly doped silicon for direct integration in large area displays.     

Optimizing reaction condition for synthesizing spinnable carbon nanotube arrays by chemical vapor deposition

Compared with the ordinary vertically aligned carbon nanotube (VACNT) arrays, the carbon nanotubes in spinnable VACNT arrays have better alignment, higher density, and narrower diameter distribution. The synthesis of spinnable VACNT arrays is sensitive to the reaction condition and the repeatable prepared of spinnable VACNT arrays still need improvement. In this paper, spinnable VACNT arrays were grown by chemical vapor deposition from C₂H₂/Ar using Fe coated on Si wafers as a catalyst. With the aim of improving the yield and reproducibility of spinnable VACNT arrays, the reaction conditions were systematically investigated. The growth kinetics of VACNT arrays was also investigated. The rate of growth of VACNT arrays can reach 465 μm/min at the initial growth stage and the activation energy of VACNT array growth is determined to be 112.2 kJ/mol. Meanwhile, a collective growth model for the evolution of spinnable VACNT arrays is also proposed.     

The effect of substrate morphology on the diameter distribution of carbon nanotubes grown on silica and ceramic substrates

Large-scale well-aligned carbon nanotube film and carbon nanotube bundles have been fabricated on smooth silica and rough polycrystalline ceramic substrates by pyrolysis of ferrocene/melamine mixtures. The images of transmission electron microscopy (TEM) and scanning electron microscope (SEM) show that carbon nanotubes grown on the silica substrate have uniform outer diameters of about ∼ 25 nm and lengths of about 40 μm, while those on the ceramic substrate have outer diameters from 10 to 90 nm and lengths up to 100 μm. Electron energy-loss spectroscopy (EELS) spectra show that nanotubes grown on the two different substrates are pure carbon tubes. The effects of substrate micro-morphologies on the diameters of carbon nanotubes have been discussed.     

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.     

Wafer-Scale Growth and Transfer of Aligned Single-Walled Carbon Nanotubes

Experimental demonstration of wafer-scale growth of well-aligned, dense, single-walled carbon nanotubes on 4" ST-cut quartz wafers is presented. We developed a new carbon nanotube (CNT) wafer-scale growth process. This process allows quartz wafers to be heated to the CNT growth temperature of 865degC through the alpha-beta phase transformation temperature of quartz (573degC) without wafer fracture. We also demonstrate wafer-scale CNT transfer to transfer these aligned CNTs from quartz wafers to silicon wafers. The CNT transfer process preserves CNT density and alignment. Carbon nanotube FETs fabricated using these transferred CNTs exhibit high yield. Wafer-scale growth and wafer-scale transfer of aligned CNTs enable carbon nanotube very large-scale integration circuits and their large-scale integration with silicon CMOS.     

Investigation of influence of synthesis parameters on length and purity of the carbon nanotubes

In this article, a systematic study was conducted to understand the influences of various synthesis parameters, such as catalyst pretreatment time, growth time, growth temperature, reaction gas flow rate on length and quality of the carbon nanotubes grown by thermal chemical vapor deposition (TCVD). Carbon nanotube (CNT) grown on Fe deposited on silicon substrates were characterized by scanning electron microscope and Raman spectroscopy. It was found that all of the synthesis parameters investigated had effects on both length and quality of the carbon nanotube. After optimizing the various thermal chemical vapor deposition synthesis parameters, long carbon nanotube arrays of up to 150 microm in length were successfully synthesized and possess the potential application in multi-level interconnects.     

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.     

Photovoltaic response of carbon nanotube-silicon heterojunctions: effect of nanotube film thickness and number of walls

We report on the multiwall carbon nanotube application as energy conversion material to fabricate thin film solar cells, with nanotubes acting as photogeneration sites as well as charge separators, collectors and carrier transporters. The device consists of a semitransparent thin film of nanotubes coating a n-type crystalline silicon substrate. Under illumination electron-hole (e-h) pairs, generated in the nanotubes and in the silicon substrate underneath, are split and charges are transported through the nanotubes (electrons) and the n-Si (holes). We found that a suitable thickness of the nanotube thin film, high density of Schottky junctions between nanotubes and n-Si and lowest number of nanotube walls are all fundamental parameters to improve the device incident photon to electron conversion efficiency. Multiwall carbon nanotubes have been synthesized by chemical vapour deposition in an ultra high vacuum chamber by evaporating a given amount of iron at room temperature and then exposing the substrate kept at 800 degrees C at acetylene gas. The amount of deposited iron is found to directly affect the nanotube size distribution (inner and outer diameter) and therefore the number of walls of the nanotubes.     

Tunable field emission properties of carbon nanotube arrays by engineering Fe catalysts

High-quality carbon nanotube (CNT) arrays composed of nanotubes with different diameters and wall numbers were synthesized by water-assisted chemical vapor deposition (CVD) from engineered Fe catalysts. Interestingly, the distribution of nanotube diameter and wall number broadened over 2.5 times as the catalytic Fe thickness increased. The mean diameter and wall number of nanotubes increased monotonically with the Fe thickness, while the calculated CNT area density within an array dropped about 32 times. Field emission measurements revealed that the turn-on voltage for CNT arrays decreased from 3.5 to 2.5 V/µm with the increased catalytic Fe thickness. It was believed that the screening effect from the proximity of neighboring nanotubes has a dominant influence than the CNT diameter on the resulting turn-on voltage.     

Adhesion between two radially collapsed single-walled carbon nanotubes

Continuum mechanics analysis and molecular mechanics simulations are performed to study adhesion between two identical, radially collapsed single-walled carbon nanotubes. Not only the inter-adhesion energy between nanotubes but also the inner adhesion energy in a nanotube is considered. A closed-form solution to the adhesion configuration is achieved, which is well consistent with our molecular mechanics simulation. Comparing the potential energy of the adhesion structures formed by two identical single-walled carbon nanotubes, three types of configurations, i.e., circular, deformed, and collapsed shape, will be formed with increasing carbon nanotubes radius and separated by two critical radii of the single-walled carbon nanotube. Furthermore, it is found that the collapsed adhesion structure possesses the highest interfacial adhesion energy. The results demonstrate that, as a potential application in carbon nanotube reinforced composites, arrays formed by collapsed carbon nanotubes will be optimal due to the strong interface strength.     

Nanoscale memory cell based on a nanoelectromechanical switched capacitor

The demand for increased information storage densities has pushed silicon technology to its limits and led to a focus on research on novel materials and device structures, such as magnetoresistive random access memory and carbon nanotube field-effect transistors, for ultra-large-scale integrated memory. Electromechanical devices are suitable for memory applications because of their excellent 'ON-OFF' ratios and fast switching characteristics, but they involve larger cells and more complex fabrication processes than silicon-based arrangements. Nanoelectromechanical devices based on carbon nanotubes have been reported previously, but it is still not possible to control the number and spatial location of nanotubes over large areas with the precision needed for the production of integrated circuits. Here we report a novel nanoelectromechanical switched capacitor structure based on vertically aligned multiwalled carbon nanotubes in which the mechanical movement of a nanotube relative to a carbon nanotube based capacitor defines 'ON' and 'OFF' states. The carbon nanotubes are grown with controlled dimensions at pre-defined locations on a silicon substrate in a process that could be made compatible with existing silicon technology, and the vertical orientation allows for a significant decrease in cell area over conventional devices. We have written data to the structure and it should be possible to read data with standard dynamic random access memory sensing circuitry. Simulations suggest that the use of high-k dielectrics in the capacitors will increase the capacitance to the levels needed for dynamic random access memory applications.     

Template-based synthesis and magnetic properties of Ni nanotube arrays with different diameters

Ni nanotube arrays with different diameters were fabricated in the pores of the porous anodic alumina membranes by direct current electrodeposition. The crystal structure and micrograph of Ni nanotube arrays were characterized by X-ray diffraction, transmission electron microscopy, and field-emission scanning electron microscopy. The results indicate that Ni nanotubes have no preferred orientation and are polycrystalline structure. The magnetic behaviors of Ni nanotube arrays with different diameters are investigated, and the coercivity of Ni nanotubes depends strongly on their diameters. The size-dependent behavior of the coercivity is qualitatively explained in terms of localized magnetization reversal.     

碳纳米管阵列制备及结构与光学特性研究

以乙烯为碳源,铁为催化剂,通过调节碳源气体的供给时间来控制碳纳米管阵列的生长过程,最终在负载有催化剂膜层的硅基底上生长出不同高度的碳纳米管阵列,经sEM、TEM、激光拉曼和紫外-可见-近红外分光光度计对其结构和特性进行分析,结果表明,碳纳米管阵列在300nm-2000nm范围可以达到小于0．238％的超低反射率,不同结构和高度的碳纳米管阵列表现出不同的紫外-可见-近红外反射特性。     

Micromachined silicon transmission electron microscopy grids for direct characterization of as-grown nanotubes

Transmission electron microscopy (TEM) is a key technique in the structural characterization of carbon nanotubes. For device applications, carbon nanotubes are typically grown by chemical vapour deposition (CVD) on silicon substrates. However, TEM requires very thin samples, which are electron transparent. Therefore, for TEM analysis, CVD grown nanotubes are typically deposited on commercial TEM grids by post-processing. However, this procedure can damage the nanotubes, and it does not work reliably if the nanotube density is too low. The ability to do TEM directly on as-grown nanotubes on the silicon substrate would solve these problems. For this purpose, we have fabricated micromachined silicon TEM grids with narrow open slits on them. Since the nanotubes grown on these substrates are suspended freely over the open slits, the micromachined substrates form a natural TEM grid for direct imaging of CVD grown nanotubes. Furthermore, the background noise is significantly reduced during micro-Raman spectroscopy, resulting in a better signal-to-noise ratio. As a result, these micromachined Si substrates provide a low cost, mass producible, efficient, and reliable platform for direct TEM, SEM, AFM, and Raman characterization of as-grown nanotubes. These grids can be used for characterizing a wide range of other nanomaterials, including peapods, nanowires, and nanofibres.     

Nanobarrier-terminated growth of single-walled carbon nanotubes on quartz surfaces

Using carbon nanotubes as nanobarriers, the growth of single-walled carbon nanotubes (SWNTs) on a quartz surface can be terminated. First, carbon nanotube nanobarriers were grown on a quartz surface by the gas flow-directed growth mode. Then, the SWNTs were grown on the quartz surface via the lattice-oriented growth mode, in which growth of SWNTs can be terminated by hitting the nanotube nanobarriers. Moreover, using the carbon nanotube nanobarrier as a marker, the mechanism of the growth of SWNTs on the quartz surface can be studied; a base-growth mechanism is indicated. Based on this termination process and the base-growth mechanism, SWNT arrays with controlled lengths can be grown on a quartz surface by fixing the sites of both catalysts and nanobarriers.      

Synthesis of carbon nanotubes using Ni95Ti5 nanocrystalline film as a catalyst

Carbon nanotubes (CNTs) were synthesized by low-pressure chemical vapour deposition (LPCVD) using N2:C2H2:H2 gas mixtures on nanocrystalline Ni95Ti5 film. This nanocrystalline film was deposited on silicon substrate using vapour condensation method. The growth temperature and growth time was kept at 800 degrees C and 30 mins, respectively and the pressure was maintained at 10 Torr. The growth mechanism of CNTs was investigated using FESEM, TEM, HRTEM, and Raman Spectroscopy. From FESEM image of Ni95Ti5 nanocrystalline film, it is clear that the particle size varies from 5-10 nm. EDX analysis suggests that Ni95Ti5 alloy contains Ni and Ti both. It is clear from TEM images that CNTs are multiwalled with the diameter varying from 10-30 nm and length of several micrometers. HRTEM image shows that the structure of these multi-walled nanotube (MWNTs) is bamboo-shaped and the catalyst exists at the tip of MWNTs. Fourier Transform Raman Spectroscopy confirmed that graphitic structure of as-prepared CNTs. Field emission measurements reveal that the carbon nanotubes grown for 30 mins showed a turn-on field of 7.2 V/microm, when the current density achieves 10 microA/cm2. The field enhancement factor was calculated to be 708.50 for carbon nanotubes grown for 30 mins.     

An atlas of carbon nanotube optical transitions

Electron-electron interactions are significantly enhanced in one-dimensional systems, and single-walled carbon nanotubes provide a unique opportunity for studying such interactions and the related many-body effects in one dimension. However, single-walled nanotubes can have a wide range of diameters and hundreds of different structures, each defined by its chiral index (n,m), where n and m are integers that can have values from zero up to 30 or more. Moreover, one-third of these structures are metals and two-thirds are semiconductors, and they display optical resonances at many different frequencies. Systematic studies of many-body effects in nanotubes would therefore benefit from the availability of a technique for identifying the chiral index of a nanotube based on a measurement of its optical resonances, and vice versa. Here, we report the establishment of a structure-property 'atlas' for nanotube optical transitions based on simultaneous electron diffraction measurements of the chiral index and Rayleigh scattering measurements of the optical resonances of 206 different single-walled nanotube structures. The nanotubes, which were suspended across open slit structures on silicon substrates, had diameters in the range 1.3-4.7?nm. We also use this atlas as a starting point for a systematic study of many-body effects in the excited states of single-walled nanotubes. We find that electron-electron interactions shift the optical resonance energies by the same amount for both metallic and semiconducting nanotubes, and that this shift (which corresponds to an effective Fermi velocity renormalization) increases monotonically with nanotube diameter. This behaviour arises from two sources: an intriguing cancellation of long-range electron-electron interaction effects, and the dependence of short-range electron-electron interactions on diameter.     

Electrochemically grown Pd nanoparticles used for synthesis of carbon nanotube by microwave plasma enhanced chemical vapor deposition

Pd nanoparticles of well-defined shapes with face centered cubic structure were grown electrochemically on silicon substrates with high degree of reproducibility. As direct application of these electrochemically grown Pd nanostructures they have been used as catalyst for the growth of multi wall carbon nanotube (MWCNT). It is observed that the MWCNTs are filled with a Pd based material during growth by microwave plasma enhanced chemical vapor deposition (MPECVD) technique. High-resolution transmission electron microscopy, used to study the material inside MWCNT suggests the formation of PdH0.649 or Pd2Si during the growth of carbon nanotube. Raman spectroscopy has been used to study the structure of the MPECVD grown carbon nanotubes.