Frequency characteristics of field electron emission from long carbon nanofilaments/nanotubes in a weak AC electric field

Frequency characteristics of field electron emission from long carbon nanofilaments/nanotubes in strong dc and weak ac electric fields have been investigated. A series of narrow peaks with a quality factor of up to 1100 has been discovered in the frequency range of hundreds of kilohertz. The analysis has shown that these peaks are probably associated with mechanical oscillations of the carbon nanofilaments/nanotubes driven by the ac electric field.     

Mechanism of field electron emission from carbon nanotubes

Field electron emission (FE) is a quantum tunneling process in which electrons are injected from materials (usually metals) into a vacuum under the influence of an applied electric field. In order to obtain usable electron current, the conventional way is to increase the local field at the surface of an emitter. For a plane metal emitter with a typical work function of 5 eV, an applied field of over 1 000 V/μm is needed to obtain a significant current. The high working field (and/or the voltage between the electrodes) has been the bottleneck for many applications of the FE technique. Since the 1960s, enormous effort has been devoted to reduce the working macroscopic field (voltage). A widely adopted idea is to sharpen the emitters to get a large surface field enhancement. The materials of emitters should have good electronic conductivity, high melting points, good chemical inertness, and high mechanical stiffness. Carbon nanotubes (CNTs) are built with such needed properties. As a quasi-one-dimensional material, the CNT is expected to have a large surface field enhancement factor. The experiments have proved the excellent FE performance of CNTs. The turn-on field (the macroscopic field for obtaining a density of 10 μA/cm²) of CNT based emitters can be as low as 1 V/μm. However, this turn-on field is too good to be explained by conventional theory. There are other observations, such as the non-linear Fowler-Nordheim plot and multi-peaks field emission energy distribution spectra, indicating that the field enhancement is not the only story in the FE of CNTs. Since the discovery of CNTs, people have employed more serious quantum mechanical methods, including the electronic band theory, tight-binding theory, scattering theory and density function theory, to investigate FE of CNTs. A few theoretical models have been developed at the same time. The multi-walled carbon nanotubes (MWCNTs) should be assembled with a sharp metal needle of nano-scale radius, for which the FE mechanism is more or less clear. Although MWCNTs are more common in present FE applications, the single-walled carbon nanotubes (SWCNTs) are more interesting in the theoretical point of view since the SWCNTs have unique atomic structures and electronic properties. It would be very interesting if people can predict the behavior of the well-defined SWCNTs quantitatively (for MWCNTs, this is currently impossible). The FE as a tunneling process is sensitive to the apex-vacuum potential barrier of CNTs. On the other hand, the barrier could be significantly altered by the redistribution of excessive charges in the micrometer long SWCNTs, which have only one layer of carbon atoms. Therefore, the conventional theories based upon the hypothesis of fixed potential (work function) would not be valid in this quasi-one-dimensional system. In this review, we shall focus on the mechanism that would be responsible for the superior field emission characteristics of CNTs. We shall introduce a multi-scale simulation algorithm that deals with the entire carbon nanotube as well as the substrate as a whole. The simulation for (5, 5) capped SWCNTs with lengths in the order of micrometers is given as an example. The results show that the field dependence of the apex-vacuum electron potential barrier of a long carbon nanotube is a more pronounced effect, besides the local field enhancement phenomenon.     

Stable electron field emission from carbon nanotubes emitter transferred on graphene films

Carbon nanotubes (CNTs) arrays grown by microwave plasma enhanced chemical vapor deposition (MPCVD) method was transferred onto the substrate covered with graphene layer obtained by thermal chemical vapor deposition (CVD) technology. The graphene buffer layer provides good electrical and thermal contact to the CNTs. The field emission characteristics of this hybrid structure were investigated in this study. Compared with the CNTs arrays directly grown on the silicon substrate, the hybrid emitter shows better field emission performance, such as high emission current and long-term emission stability. The presence of this graphene layer was shown to improve the field emission behavior of CNTs. This work provides an effective way to realize stable field emission from CNTs emitter and similar hybrid structures.     

Carbon nanofibers and multiwalled carbon nanotubes from camphor and their field electron emission

Vertically aligned carbon nanofibers (CNF) and multiwalled carbon nanotubes (MWCN) have been synthesized from camphor by catalytic thermal CVD method on Co and Co/Fe thin films (for CNF) and on silicon substrates using a mixture of camphor and ferrocene (for MWCN). CNF and MWCN are studied by field emission scanning electron microscopy, high-resolution transmission electron microscopy, visible Raman spectroscopy, X-ray diffraction in order to get insight into the microstructure and morphology of these materials. Field electron emission study indicates turn-on field of about 2.56, 3.0 and 6.5 V/μm for MWCN, Co/CNF and Co/Fe/CNF films, respectively. The best performance of MWCN in field electron emission among the materials studied can be due to the highest aspect ratio, good graphitization and good density.     

Influence of cesium atoms on the field electron emission from multi-walled carbon nanotubes

It has been shown that the deposition of cesium atoms on multi-wall carbon nanotubes abruptly increases the current of the field electron emission, decreases the threshold electric field by a factor of three (to 0.8 V/m), and decreases the work function to 2.1–2.3 eV. It has been found that the flowing of the large emission current I ≥ 2 × 10^?6 A leads to a change in the current-voltage characteristics and a decrease in the emission current. This effect has been explained by escape of cesium atoms from the tips of most nanotubes into the nanotube depth due to desorption or intercalation. At the same time, the low work function is retained for some nanotubes, probably, due to the stronger bonding of Cs atoms with these nanotubes.     

Thermal instability of field emission from carbon nanotubes

The mechanism that limits the emission current of a carbon-nanotube-based cathode due to the temperature dependence of the emissivity of the nanotube is studied. This limitation has the character of thermal instability that shows up as an infinite increase in the emitter temperature after a certain emission current is exceeded. The heat conduction equation is solved for a nanotube at various model temperature dependences of the thermal and electrical conductivities of the nanotube in order to derive the limiting emission current as a function of the electrical conductivity of the nanotube.     

碳纳米管场致电子发射新机制

基于对长达 1μm的 (5 ,5 )碳纳米管的量子力学计算 ,作者发现使碳纳米管具有优异场致电子发射特性的因素除了人们预期的尖端场增强之外 ,电荷在纳米管尖端的积累造成有效功函数 (真空势垒 )的非线性下降也起了非常重要的作用 .对外加电场Vappl=10— 14V/ μm下的碳纳米管进行了计算 ,得到与实验结果相近的发射电流     

Effect of temperature on the electron field emission from aligned carbon nanofibers and multiwalled carbon nanotubes

Effect of temperature and aspect ratio on the field emission properties of vertically aligned carbon nanofiber and multiwalled carbon nanotube thin films were studied in detail. Carbon nanofibers and multiwalled carbon nanotube have been synthesized on Si substrates via direct current plasma enhanced chemical vapor deposition technique. Surface morphologies of the films have been studied by a scanning electron microscope, transmission electron microscope and an atomic force microscope. It is found that the threshold field and the emission current density are dependent on the ambient temperature as well as on the aspect ratio of the carbon nanostructure. The threshold field for carbon nanofibers was found to decrease from 5.1 to 2.6 V/μm when the temperature was raised from 300 to 650 K, whereas for MWCNTs it was found to decrease from 4.0 to 1.4 V/μm. This dependence was due to the change in work function of the nanofibers and nanotubes with temperature. The field enhancement factor, current density and the dependence of the effective work function with temperature and with aspect ratio were calculated and we have tried to explain the emission mechanism.     

Low-voltage nonstationary electron emission from single-walled carbon nanotubes as exoelectron emission

Low-voltage nonstationary electron emission from single-walled carbon nanotubes after the passage of high autoemission current has been observed. This emission is assumed to be exoelectron emission associated with mechanical stresses and defects appearing in nanotubes due to electrostatic forces acting on nanotubes in a strong electric field.     

Effect of adsorbates on field emission from carbon nanotubes

Recent experiments indicate that water molecules adsorbed on carbon nanotube tips significantly enhance field-emission current. Through first-principles density-functional theory calculations we show that the water-nanotube interaction is weak in zero electric field. However, under emission conditions large electric field present at the tube tip: (a) increases the binding energy appreciably, thereby stabilizing the adsorbate; and (b) lowers the ionization potential (IP), thereby making it easier to extract electrons. Lowering of IP is enhanced further through the formation of a water cluster on the nanotube tip.     

Field electron emission from carbon nanotubes in the presence of a weak high-frequency electric field

Series of narrow peaks in the frequency range of f ≈ 50–1200 MHz have been revealed in the frequency responses of the emission current from carbon nanotubes in the presence of a weak high-frequency electric field. The analysis makes it possible to attribute these peaks to resonance of the first and second harmonics of forced mechanical vibrations of carbon nanotubes in a high-frequency electric field. The determined Q factor of nanotubes is in the range of 100–300.     

Electron field emission from magnetic nanomaterial encapsulated multi-walled carbon nanotubes

The present work describes the field emission characteristics of nanoscale magnetic nanomaterial encapsulated multi-walled carbon nanotubes (MWNTs) fabricated over flexible graphitized carbon cloth. Ni/MWNTs, NiFe/MWNTs and NiFeCo/MWNTs have been synthesized by catalytic chemical vapor decomposition of methane over Mischmetal (Mm)-based AB₃ (MmNi₃, MmFe_1.5Ni_1.5 and MmFeCoNi) alloy hydride catalysts. Metal-encapsulated MWNTs exhibited superior field emission performance than pure MWNT-based field emitters over the same substrate. The results indicate that a Ni-filled MWNT field emitter is a promising material for practical field emission application with a lowest turn-on field of 0.6 V/μm and a high emission current density of 0.3 mA/cm² at 0.9 V/μm.     

Field electron emission images of multi-walled carbon nanotubes

Field electron emission microscope images from multi-walled carbon nanotubes can typically be characterized by the presence of five pentagons surrounding a sixth central pentagon. The observations of bright line centered interference patterns between adjacent pentagons in the field electron emission microscope images of multi-walled carbon nanotubes have been reported in the literature. We have observed a shift from bright to dark line centered interference patterns and associated this with the presence of surface adsorption. In order to identify the origin of the contaminant, multi-walled carbon nanotubes were dosed with H₂, H₂O, CO and O₂ and then imaged in the field electron emission microscope. Only the samples exposed to O₂ showed a shift from a bright line centered pattern between adjacent pentagons of a clean surface to a dark line centered pattern when one pentagon was contaminated or a bright line centered pattern when both adjacent pentagons become contaminated. The results of the experimental studies and the modeling of the changes in the field emission pattern as phase shifts in the wave function of the tunneling electrons due to modifications in the surface work function are presented.     

High-field electron emission of carbon nanotubes grown on carbon fibers

Carbon nanotubes with uniform density were synthesized on carbon fiber substrate by the floating catalyst method. The morphology and microstructure were characterized by scanning electron microscopy and Raman spectroscopy. The results of field emission showed that the emission current density of carbon nanotubes/carbon fibers was 10 μA/cm² and 1 mA/cm² at the field of 1.25 and 2.25 V/μm, respectively, and the emission current density could be 10 and 81.2 mA/cm² with the field of 4.5 and 7 V/μm, respectively. Using uniform and sparse density distribution of carbon nanotubes on carbon fiber substrate, the tip predominance of carbon nanotubes can be exerted, and simultaneously the effect of screening between adjacent carbon nanotubes on field emission performance can also be effectively decreased. Therefore, the carbon nanotubes/carbon fibers composite should be a good candidate for a cold cathode material.     

镜像势对碳纳米管阵列场发射特性的影响

采用多尺度量子化学方法模拟了碳纳米管阵列的场发射特性.碳纳米管镜像势的作用可以等效地用原子尺寸的理想金属球的镜像势来代替.模拟计算结果表明,考虑了镜像势作用后的碳纳米管阵列发射电流密度比没有考虑镜像势的结果增大了约6倍. 关键词： 镜像势 碳纳米管 场致发射     

纳米碳管阵列场发射电流密度的理论数值优化

以纳米碳管阵列为研究对象,利用镜像悬浮球模型及Fowler-Nordheim电流密度公式,对纳米碳管阵列的场发射电流密度进行计算,进而综合考虑场发射增强因子及场发射电流密度对纳米碳管阵列场发射性能进行定量优化.参考碳管阵列场发射电流密度最大值及场发射增强因子,表明当纳米碳管阵列间距为碳管高度十分之一时,纳米碳管阵列的场发射性能得到优化.与以前的理论估算结果相比,优化的阵列间距进一步减小.当纳米碳管间距过大,场发射增强因子增加,而场发射电流密度会在更大程度上减小;当纳米碳管密度较大时,场发射增强因子受到静电 关键词： 纳米碳管 场发射 增强因子 电流密度     

Electron field emission properties of closed carbon nanotubes

Recent experiments have shown that carbon nanotubes exhibit excellent electron field emisson properties with high current densities at low electric fields. Here we present theoretical investigations that incorporate geometrical effects and the electronic structure of nanotubes. The electric field is dramatically enhanced near the cap of a nanotube with a large variation of local field distribution. It is found that deviation from linear Fowler-Nordheim behavior occurs due to the variation of the local field in the electron tunneling region. The maximum current per tube is of the order of 10 microA. Local and microscopic aspects of field emission from nanotubes are also presented.     

Electron emission from arrays of carbon nanotubes/fibres

The overall aim of this work is to produce arrays of field emitting microguns, based on carbon nanotubes, which can be utilised in the manufacture of large area field emitting displays, parallel e-beam lithography systems and electron sources for high frequency amplifiers. This paper will describe the work carried out to produce patterned arrays of aligned multiwall carbon nanotubes (MWCNTs) using a dc plasma technique and a Ni catalyst. We will discuss how the density of the carbon nanotube/fibres can be varied by reducing the deposition yield through nickel interaction with a diffusion layer or by direct lithographic patterning of the Ni catalyst to precisely define the position of each nanotube/fibre. Details of the field emission behaviour of the different arrays of MWCNTS will also be presented.     

Field emission from multi-walled carbon nanotubes and its application to electron tubes

Received: 5 December 1997     

Optimization of field emission properties from multi-walled carbon nanotubes using ceramic fillers

The field emission properties of multi-walled carbon nanotubes were examined using a screen-printed thick film with a diode-type configuration in a vacuum. The effects of various concentrations of two different ceramic fillers, indium tin oxide (ITO) powder and a glass frit, on the emission current density and turn-on field were evaluated. The emission properties of both pastes were dependent on the amount of filler. Considerably enhanced emission properties were obtained with the paste containing 5–10 wt.% of either ITO or the glass frit compared with those without a filler. The paste containing the ceramic filler showed enhanced emission properties compared with that containing the 5 wt.% Ag conventionally used, which confirmed the importance of the filler. The paste containing 10 wt.% ITO represented an emission current density of 176.4 μA/cm² at 5 V/μA, a turn-on field of 1.87 V/μA for an emission current density of 1 μA/cm² and a field enhancement factor of 7580. The paste formulation was also found to be suitable for fine patterning using UV-lithography techniques. A long-term stability test for 110 h of a paste containing 10 wt.% ITO revealed a half-life of approximately 30000 h, which is appropriate for commercial applications.