Improving the field-emission properties of carbon nanotubes by magnetically controlled nickel-electroplating treatment

A novel magnetically controlled Ni-plating method has been developed to improve the field-emission properties of carbon nanotubes (CNTs). The effect of the magnetic field and Ni-electroplating on CNT field-emission properties was investigated, and the results are demonstrated using scanning electron microscopy, J-E and the duration test. After treatment, the turn-on electric field declines from 1.55 to 0.91 V/μm at an emission current density of 100 μA/cm², and the emission current density increases from 0.011 to 0.34 mA/cm² at an electric field of 1.0 V/μm. Both the brightness and uniformity of the CNT emission performance are improved after treatment.     

Electron emission studies of CNTs grown on Ti and Ni containing amorphous carbon nanocomposite films

Carbon nanotubes (CNTs) were grown successfully on the as-deposited dual metal (Ti and Ni) embedded films using a radio frequency plasma-enhanced chemical vapor deposition system. The microstructure of CNTs grown on the dual metal films proved to be heavily dependent on the percentages of metals included, varying both in size and in density. Electron emission tests carried out on the films with CNTs grown showed that the threshold field was dependent on the surface morphology of the CNTs, with the lowest threshold field at 3.5 V/μm from 2.5% Ti/Ni film with CNTs. The field enhancement factor, β, of the emitting tips was also calculated from the Fowler–Nordheim plots, where CNTs from the 2.5% Ti/Ni film gave the highest field enhancement factor. However, it was observed that films with a single metal of either Ti or Ni did not manage to grow CNTs, possibly due to a lack of catalyst centres at the surface of the films. It was believed that the Ni nanoclusters acted as catalysts centres giving a rather uniform but randomly orientated type of CNTs. Results obtained pointed that the fabricated nanocomposite material could be a possible choice for cold cathode emitters and the Ti/Ni mixture could be an effective composite for controlling the CNT density.     

Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites

Carbon nanotubes (CNTs) were controllably coated with the uninterrupted CuO and CeO₂ composite nanoparticles by a facile pyridine-thermal method and the high catalytic performance for CO oxidation was also found. The obtained nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction as well as X-ray photoelectron spectroscopy. It is found that the CuO/CeO₂ composite nanoparticles are distributed uniformly on the surface of CNTs and the shell of CeO₂/CuO/CNT nanocomposites is made of nanoparticles with a diameter of 30-60 nm. The possible formation mechanism is suggest as follows: the surface of CNTs is modified by the pyridine due to the π-π conjugate role so that the alkaline of pyridine attached on the CNT surface is more enhanced as compared to the one in the bulk solvent, and thus, these pyridines accept the proton from the water molecular preferentially, which result in the formation of the OH⁻ ions around the surface of CNTs. Subsequently, the metal ions such as Ce³⁺ and Cu²⁺ in situ react with the OH⁻ ions and the resultant nanoparticles deposit on the surface of CNTs, and finally the CeO₂/CuO/CNT nanocomposites are obtained. The T₅₀ depicting the catalytic activity for CO oxidation over CeO₂/CuO/CNT nanocomposites can reach ∼113 °C, which is much lower than that of CeO₂/CNT or CuO/CNT nanocomposites or CNTs.     

A comparative study of thermionic emission from vertically grown carbon nanotubes and tungsten cathodes

Thermionic emission from vertically grown carbon nanotubes (CNTs) by water-assisted chemical vapor deposition (WA-CVD) is investigated. I-V characteristics of WA-CNT samples exhibit strong Schottky effect leading to field proportionality factor β ∼ 10⁴ cm⁻¹in contrast to β ∼ 200 cm⁻¹ for the bare tungsten substrate. Non-contact atomic force microscopy imaging of CNT samples show propensity of nanoasperities over a scale of micron size over which the tungsten surface is seen to be atomically smooth. The values of root mean-square roughness for CNTs and W were found to be 24.2 nm and 0.44 nm respectively. The Richardson-Dushman plots yield work function values of Φ_CNT ? 4.5 and Φ_W ? 4.3 eV. Current versus time data shows that CNT cathodes are fifteen times noisier than tungsten cathode presumably due to increased importance of individual atomic events on the sharp CNT tips of bristle like structures. Power spectral density of current exhibited 1/f^ξ behavior with ξ ? 1.5, and 2 for W and CNTs. The former suggests surface diffusion whereas the latter indicates adsorption/desorption of atomic/molecular species as a dominant mechanism of noise generation.     

Increase of critical current density with doping carbon nano-tubes in YBa2Cu3O7−δ

The effects of carbon nano-tubes (CNTs) on the crystal structure and superconducting properties of YBa₂Cu₃O_7?δ (Y-123) compound were studied. Samples were synthesized using standard solid-state reaction technique by adding CNT up to 1 wt% and X-ray diffraction data confirm the single phase orthorhombic structure for all the samples. Current–voltage measurements in magnetic fields up to 9 T were used to study the pinning energy U_J and critical current density J_c as a function of magnetic field at fixed temperature. We find that while T_c does not change much with the CNT doping (91–92 K), both U_J and J_c increase systematically up to 0.7 wt% CNT doping in a broad magnetic field ranges between 0.1 and 9 T and J_c in the 0.7 wt% CNT doped sample is at least 10 times larger than that of the pure Y-123. The scanning electron microscope image shows that CNTs are forming an electrical-network between grains. These observations suggest that the CNT addition to the Y-123-compounds improve the electrical connection between superconducting grains to result in the J_c increase.     

Dynamic evolution of interacting carbon nanotubes suspended in a fluid using a dielectrophoretic framework

A theoretical investigation of the dynamic response of interacting carbon nanotubes (CNTs) dispersed in a liquid medium under alternating current electric fields is presented. The proposed modeling strategy is based on the dielectrophoretic theory and classical electrodynamics of rigid bodies, and considers the coupled rotation-translation motion of interacting CNTs represented as electrical dipoles. Based on experimental evidence, the parameters which are expected to cause a major contribution to the CNTs' motion are investigated for different initial configurations of CNTs. It is predicted that high electric field frequencies, long CNTs, high values of electrical permittivity and conductivity of the CNTs immersed in solvents of high polarity promote faster equilibrium conditions, achieved by CNT tip-to-tip contact and alignment along the electric field direction. For the majority of the scenarios, CNT alignment along the field direction is predicted as the first event, followed by the translation of aligned CNTs until the tip-to-tip contact condition is reached. For systems with interacting CNTs with different lengths, equilibrium of the shorter CNT is achieved faster. Predictions also show that the initial rotation angles and initial location of CNTs have a paramount influence on the evolution of the system towards the equilibrium configuration.     

Purification of carbon nanotubes grown by thermal CVD

We show the results of a set of purifications on carbon nanotubes (CNT) by acid and basic treatments. CNTs were obtained by thermal decomposition of camphor at 850 °C in a CVD growth system, by means of a growth process catalyzed by iron clusters originating from the addition of ferrocene in the precursors mixture. The purification procedures involved HNO₃, H₂SO₄, HSO₃Cl and NaOH for different process temperatures.As-grown CNTs showed a consistent presence of metal catalyst (about 6 wt%), evidenced by TGA. The purification treatments led to a certain amount of opening of the CNT tips, with a consequent loss of metal catalyst encapsulated in tips. This is also confirmed by BET analysis, which showed an increase of the surface area density of CNT after the purification.FT-IR and XPS revealed the presence of carboxylic groups on the CNT surface chemically modified by the harsh environment of the purification process.Among the various treatments that have been tested, the 1:3 solution of nitric and sulphuric acid was the most effective in modifying the CNT surface and inducing the formation of functional groups.     

Structural and electronic properties of endohedral doped SWCNTs: A DFT study

The structural and electronic properties of semiconductors (Si and Ge) and metal (Au and Tl) atoms doped armchair (n, n) and zigzag (n, 0); n=4–6, single wall carbon nanotubes (SWCNTs) have been studied using an ab-initio method. We have considered a linear chain of dopant atoms inside CNTs of different diameters but of same length. We have studied variation of B.E./atom, ionization potential, electron affinity and HOMO–LUMO gap of doped armchair and zigzag CNTs with diameter and dopant type. For armchair undoped CNTs, the B.E./atom increases with the increase in diameter of the tubes. For Si, Ge and Tl doped CNTs, B.E./atom is maximum for (6, 6) CNT whereas for Au doped CNTs, it is maximum for (5, 5) CNTs. For pure CNTs, IP decreases slightly with increasing diameter whereas EA increases with diameter. The study of HOMO–LUMO gap shows that on doping metallic character of the armchair CNTs increases whereas for zigzag CNTs semiconducting character increases. In case of zigzag tubes only Si doped (5, 0), (6, 0) and Ge doped (6, 0) CNTs are stable. The IP and EA for doped zigzag CNTs remain almost independent of tube diameter and dopant type whereas for doped armchair CNTs, maximum IP and EA are observed for (5, 5) tube for all dopants.     

A comparative analysis of thin-film transistors using aligned and random-network carbon nanotubes

The purpose of this project is to investigate the characterization of carbon nanotube (CNT) thin-film transistors based on two solution-based fabrication methods: dielectrophoretic deposition of aligned CNTs and self-assembly of random-network CNTs. The electrical characteristics of aligned and random-network CNT transistors are studied comparatively. In particular, the selection effect of metallic and semiconducting CNTs in the dielectrophoresis process is evaluated experimentally by comparing the output characteristics of the two transistors. Our results demonstrate that the self-assembly method produces a stronger field effect with a much higher on/off ratio (I _on /I _off ). This phenomenon provides evidence that the metallic CNTs are more responsive to dielectrophoretic forces than their semiconducting counterparts under common deposition conditions. In addition, the nanotube–nanotube cross-junctions in random-network CNT films create additional energy barriers and result in a reduced electric current. Thus, additional consideration must be applied when using different fabrication methods in building CNT-based electronic devices.     

Area effect of patterned carbon nanotube bundle on field electron emission characteristics

Patterned carbon nanotube (CNT) bundles were fabricated using thermal chemical vapor deposition (CVD) method. Patterns of different diameters and distances were defined on Si(100) substrates using photolithography. CNT bundle height was controlled using different acetylene (C₂H₂) flow times. The inter-bundle distance of CNTs to CNT bundle height ratio was maintained at approximately 2, a number predicted to have a maximum field emission for CNT, and left the patterned CNT bundle area as a variable parameter. The relationship between CNT bundle area and the field electron emission characteristics was studied. The lowest threshold electric field (E_th) of 0.7 V/μm was obtained when the total area of patterned CNT bundles was approximately 46%. The result shows that there is an optimal CNT bundle area for electron field emission.     

A comparison between the mechanical and thermal properties of single-walled carbon nanotubes and boron nitride nanotubes

Carbon nanotubes (CNTs) are semimetallic while boron nitride nanotubes (BNNTs) are wide band gap insulators. Despite the discrepancy in their electrical properties, a comparison between the mechanical and thermal properties of CNTs and BNNTs has a significant research value for their potential applications. In this work, molecular dynamics simulations are performed to systematically investigate the mechanical and thermal properties of CNTs and BNNTs. The calculated Young’s modulus is about 1.1 TPa for CNTs and 0.72 TPa for BNNTs under axial compressions. The critical bucking strain and maximum stress are inversely proportional to both diameter and length-diameter ratio and CNTs are identified axially stiffer than BNNTs. Thermal conductivities of (10, 0) CNTs and (10, 0) BNNTs follow similar trends with respect to length and temperature and are lower than that of their two-dimensional counterparts, graphene nanoribbons (GNRs) and BN nanoribbons (BNNRs), respectively. As the temperature falls below 200 K (130 K) the thermal conductivity of BNNTs (BNNRs) is larger than that of CNTs (GNRs), while at higher temperature it is lower than the latter. In addition, thermal conductivities of a (10, 0) CNT and a (10, 0) BNNT are further studied and analyzed under various axial compressive strains. Low-frequency phonons which mainly come from flexure modes are believed to make dominant contribution to the thermal conductivity of CNTs and BNNTs.     

Ultraviolet-Cathodoluminescent 330 nm light source from a 2-inch wide CNT electron-beam emission under DC electric field

We report a 2-inch wide-area AlGaN-based ultraviolet (UV) – cathodoluminescence (CL) light source emission using electron beam (EB) pumped source under DC electric field from an AlGaN/GaN multi-quantum-well grown on a sapphire substrate. The EB-pumping is achieved by wide-area carbon nanotubes (CNT) based field emitters and is arranged via a metal mesh, thereby acting as a gate to pump the electron flow. We have carried out UV–CL measurements with a turn-on field emission in the anode voltage ranging between 5 kV and 9 kV at anode current up to 1 mA. The best results are obtained at the low consumption energy of 7 W (anode current 1 mA; anode voltage 7 kV). The 330 nm UV–CL emission shows an output power of ~225 mW, with an as-calculated power efficiency of ~3.6%. The CL measurements show (5–8) % defect luminescence in the visible region.     

Growth of carbon nanotubes on stainless steel substrates by DC-PECVD

We report on the fabrication of carbon nanotubes (CNTs) on Ni-coated stainless steel (SUS) substrates by using dc plasma enhanced chemical vapor deposition. The synthesized CNTs have the diameter of about 30 nm and the length of about 1.2 μm. To verify the effects of SUS substrates on the growth of CNTs, CNTs had also been grown on Ni-coated Si substrates. CNTs grown on the SUS substrates were more uniform compared with those grown on the Si substrates. Field emission properties of the CNT films were measured in the diode configuration, and the turn-on electric field of 3.87 V/μm and field enhancement factor β of about 1737 were obtained from the synthesized CNTs at the gap of 500 μm between the SUS substrate and the anode. These results have not only clarified the effects of the substrate on the growth of CNTs, but also shown the potential of CNTs in field emission applications, especially CNT-based cold-cathode X-ray tubes.     

Preparation of NiO decorated CNT/ZnO core-shell hybrid nanocomposites with the aid of ultrasonication for enhancing the performance of hybrid supercapacitors

Supercapacitor (SC) electrodes fabricated with the combination of carbon nanotubes (CNTs) and metal oxides are showing remarkable advancements in the electrochemical properties. Herein, NiO decorated CNT/ZnO core-shell hybrid nanocomposites (CNT/ZnO/NiO HNCs) are facilely synthesized by a two-step solution-based technique for the utilization in hybrid supercapacitors. Benefitting from the synergistic advantages of three materials, the CNT/ZnO/NiO HNCs based electrode has evinced superior areal capacity of ~67 µAh cm⁻² at a current density of 3 mA cm⁻² with an exceptional cycling stability of 112% even after 3000 cycles of continuous operation. Highly conductive CNTs and electrochemically active ZnO contribute to the performance enhancement. Moreover, the decoration of NiO on the surface of CNT/ZnO core-shell increases the electro active sites and stimulates the faster redox reactions which play a vital role in augmenting the electrochemical properties. Making the use of high areal capacity and ultra-long stability, a hybrid supercapacitor (HSC) was assembled with CNT/ZnO/NiO HNCs coated nickel foam (CNT/ZnO/NiO HNCs/NF) as positive electrode and CNTs coated NF as negative electrode. The fabricated HSC delivered an areal capacitance of 287 mF cm⁻² with high areal energy density (67 µWh cm⁻²) and power density (16.25 mW cm⁻²). The combination of battery type CNT/ZnO/NiO HNCs/NF and EDLC type CNT/NF helped in holding the capacity for a long period of time. Thus, the systematic assembly of CNTs and ZnO along with the NiO decoration enlarges the application window with its high rate electrochemical properties.     

钛碳化物改性碳纳米管的场发射性能

通过在碳纳米管(CNTs)表面沉积钛薄膜并经过高温真空退火处理,在CNTs表面形成了低功函数的钛碳化物.研究了钛碳化物改性CNTs的场发射性能,并利用X射线光电子能谱(XPS)对改性碳管进行了结构表征.实验结果表明,高温真空退火可使沉积在CNTs表面的钛原子与碳原子发生化学反应生成钛碳化物;经钛碳化物改性处理的CNTs的场发射性能明显改善,开启电场由改性前的121降低到104V/μm,当电场强度为234V/μm时,场发射电流密度由改性前的23增大到改性后的13.5mA/cm²,同时,CNTs的表面抗离子轰击能力增强,发射稳定性改善.对钛碳化物改性增强CNTs薄膜场发射性能的机理进行了分析. 关键词： 碳纳米管 钛碳化物 场发射 结构表征     

碳纳米管和天鹅绒阴极强流发射特性的对比研究

采用电泳沉积法、碳纳米管纸和化学气相沉积直接生长法制备了三种碳纳米管阴极. 从强流发射性能、阴极等离子体膨胀、阴极起动、发射均匀性、工作稳定性以及脉冲放气特性等多个方面, 对比研究了碳纳米管阴极和化纤天鹅绒阴极的强流发射特性, 研究表明碳纳米管阵列和碳纳米管纸阴极发射性能明显优于普通化纤天鹅绒, 碳纳米管阴极发射性能与碳纳米管取向无关, 管壁的缺陷发射对无序碳纳米管阴极强流发射具有重要贡献. 碳纳米管阴极的起动场强约为普通化纤天鹅绒的2/3, 电场上升率相同时碳纳米管阴极比化纤天鹅绒阴极起动时间短12–17 ns. 碳纳米管阴极发射均匀性优于化纤天鹅绒, 尤其是碳纳米管阵列, 整个阴极表面等离子体光斑致密且均匀. 在二极管本底气压为6×10^-3 Pa时, 碳纳米管纸阴极对应的二极管峰值气压不到0.3 Pa, 约为普通化纤天鹅绒阴极的1/5, 碳纳米管阵列阴极放气量在三种阴极中最少, 仅为0.042 Pa. 结果表明, 碳纳米管阴极在强流电子束源和相关高功率微波器件领域具有潜在的应用价值.     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

Detection and classification of host–guest interactions using β-cyclodextrin-decorated carbon nanotube-based chemiresistors

Carbon nanotubes (CNTs) in a chemiresistor setup have been widely explored in bio/chemical sensing. Detection of certain molecules with environmental and health related importance such as 9-anthracenecarboxylic acid, diclofenac sodium, and curcumin using electrochemical methods/unfunctionalized CNTs suffer from lack of response, high limit of detection (LOD) and poor selectivity. The key to overcome these issues is to decorate CNTs with host (receptor) molecules like β-cyclodextrin (β-CD) that interact with guest (target) molecules by host–guest complex formation. To improve guest recognition, and consequently, the sensor performance, effective immobilization of β-CD on the CNT surface using a non-covalent bridging molecule such as 3, 4, 9, 10-perylene tetracarboxylic acid (PTCA) is required. Furthermore, the selectivity can be assessed using the conductance correlation patterns of different host–guest systems in conjunction with a pattern classification tool. Our results indicate that PTCA linked β-CD-decorated CNT chemiresistors showed a good linear detection range (∼100 pM–100 nM), sensitivity (∼3 × 10⁻³–9 × 10⁻² nM⁻¹) and LOD (∼62 pM–101 nM), compared to devices without PTCA, in the detection of the guest molecules. The distinction in correlation patterns of different host–guest systems was corroborated by pattern classification yielding a classification accuracy, sensitivity, and specificity of ∼91.83%, ∼90.13%, and ∼85.39%, respectively.     

Superior capacitive characteristics of RuO2 nanorods grown on carbon nanotubes

Carbon nanotubes (CNTs) were used as the electric double layer capacitor (EDLC) material and were synthesized by using thermal chemical vapor deposition (TCVD). To enhance the EDLC capacity, the ruthenium dioxide (RuO₂) nanorods were grown on CNTs by using metal organic chemical vapor deposition (MOCVD). The synthesized CNTs were the principal part and template, and the RuO₂ nanorods were grown outwardly from CNTs. The increase of effective specific area between electrode and electrolyte played an important role in enhancing the capacitance. Different concentrations of KOH were used as electrolyte to measure the capacitance to find the variation of capacitance. Moreover, the RuO₂/CNT composites demonstrated a stable cycle life. The results showed that the RuO₂/CNT composites were a promising supercapacitor device material.     

Surface‐enhanced Raman scattering of pyridine‐functionalized multi‐walled carbon nanotubes

Carbon nanotubes (CNTs) have attracted great attention for their potential use in many applications because of their intrinsic properties. The importance other than the impact of the application of CNT‐embedded membranes in the area of water technology development is immense. In this context, the identification and quantification of CNTs in aqueous resources during relevant water purification processes can be proven of high significance. Surface‐enhanced Raman scattering (SERS) potentially has the sensitivity required for trace analysis and has been previously used for CNT identification on solid substrates. A thorough study for the identification and quantification of small concentrations of multi‐walled CNTs (MWCNTs) in water suspensions via SERS has been performed. The functionalization of MWCNTs with pyridine groups seems to favor the surface enhancement of relevant Raman signal. This study constitutes the first step of a work in progress for the characterization of CNTs at quite low concentration range by SERS in any water suspension. It is based on an ex ante functionalization of the CNTs by pyridine, demonstrating the potential of the method. Our long‐term aim is its general application built, however, in an ex post relevant functionalization of the CNTs in any aqueous solution. Copyright © 2014 John Wiley & Sons, Ltd.