丝网印刷制备碳纳米管阴极的强流脉冲发射特性研究

采用丝网印刷法制备了一种大面积的碳纳米管阴极,表征了阴极表面碳纳米管的形貌及分布.研究了该阴极在不同脉冲条件下的高压脉冲发射特性,分析了发射时阴极面等离子体产生和发射点的分布.研究表明：碳纳米管阴极的脉冲发射机制为爆炸电子发射,在平均场强为16.7V/μm的单脉冲电场下,阴极的最高发射电流密度为99 A/cm².在平均场强为15.4 V/μm的双脉冲电场下,阴极的最高发射电流密度为267 A/cm².碳纳米管阴极可以作为强流电子束源在高能微波器件中得到应用. 关键词： 强流脉冲电子束 碳纳米管 阴极 丝网印刷     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

一种平行背栅极碳纳米管阵列的场增强因子计算

建立一种平行背栅极碳纳米管阵列阴极,基于电场叠加原理,利用镜像电荷法对其进行计算,给出碳纳米管顶端表面电场增强因子。在此基础上,进一步分析器件各类参数对电场增强因子的影响。分析表明,碳纳米管阵列阴极具有最佳阵列密度,其对应碳纳米管间距大约为碳纳米管高度的两倍,靠阴极阵列边缘部位的碳纳米管发射电子能力比其中心部位的大。除了碳纳米管的长径比之外,栅极宽度、栅极厚度和栅极间距等也对电场增强因子有一定的影响:栅极越宽,场增强因子越大;而栅极厚度、栅极间距越大,场增强因子就越小。     

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.     

一种平行栅碳纳米管阵列阴极的场发射特性研究

建立一种平行栅碳纳米管阵列阴极,利用悬浮球模型和镜像电荷法进行计算,给出碳纳米管顶端表面电场与电场增强因子的解析式. 在此基础上,进一步分析器件各类参数以及接触电阻对阴极电子发射性能的影响. 分析表明,碳纳米管间距大约为2倍碳纳米管高度时阵列阴极的分布密度最佳,靠边缘部位的碳纳米管发射电子能力比其中心部位的大;除碳纳米管的长径比之外,栅极宽度和栅极间距也对电场增强因子有一定作用;接触电阻的存在大幅度降低碳纳米管顶端表面电场与发射电流,而接触电阻高于800 kΩ时,器件对阳极驱动电压的要求更高. 关键词： 平行栅碳纳米管阵列 悬浮球 场增强因子 接触电阻     

Electron holography of field-emitting carbon nanotubes

Electron holography performed in situ inside a high resolution transmission electron microscope has been used to determine the magnitude and spatial distribution of the electric field surrounding individual field-emitting carbon nanotubes. The electric field (and hence the associated field emission current) is concentrated precisely at the tips of the nanotubes and not at other nanotube defects such as sidewall imperfections. The electric field magnitude and distribution are stable in time, even in cases where the nanotube field emission current exhibits extensive temporal fluctuations.     

不同电场下碳纳米管场致发射电流密度研究

本文运用密度泛函理论和金属电子论, 深入研究了碳纳米管场致发射电流的变化规律. 结果显示其发射电流密度取决于体系的态密度、赝能隙、管长和局域电场, 在不同范围电场下的变化规律不同. 在较低电场下, 发射电流密度随电场增强而近似线性增大(对应的宏观电场须小于18 V· μm^-1); 但在较高电场下, 发射电流密度随外电场增加呈现非周期性振荡增长趋势, 碳纳米管表现为电离发射. 本文进一步研究了金属性碳纳米管电导率在不同电场下的变化规律.     

Lateral growth of aligned mutilwalled carbon nanotubes under electric field

In this work we report laterally aligned multi-walled carbon nanotube (MWNT) by an electric field during growth. The MWNTs were selectively grown between lateral sides of the catalytic metals on predefined electrodes by chemical-vapor deposition. The electric field distribution for various geometries was simulated using Maxwell 2D simulation in order to realize better alignment of laterally grown carbon nanotubes (CNTs). The experimental results show that the electric field direction at the vicinity of catalyst and nanotubes-substrate interactions are principal factor in aligning CNTs laterally.     

In situ measurements and modeling of carbon nanotube array growth kinetics during chemical vapor deposition

Direct measurements of carbon nanotube growth kinetics are described based upon time-resolved reflectivity (TRR) of a HeNe laser beam from vertically aligned nanotube arrays (VANTAs) as they grow during chemical vapor deposition (CVD). Growth rates and terminal lengths were measured in situ for VANTAs growing during CVD between 535 °C and 900 °C on Si substrates with evaporated Al/Fe/Mo multi-layered catalysts and acetylene feedstock at different feedstock partial pressures. Methods of analysis of the TRR signals are presented to interpret catalyst particle formation and oxidation, as well as the porosity of the VANTAs. A rate-equation model is developed to describe the measured kinetics in terms of activation energies and rate constants for surface carbon formation and diffusion on the catalyst nanoparticle, nanotube growth, and catalyst over-coating. Taken together with the TRR data, this model enables basic understanding and optimization of growth conditions for any catalyst/feedstock combination. The model lends insight into the main processes responsible for the growth of VANTAs, the measured number of walls in the nanotubes at different temperatures, conditions for growth of single-wall carbon nanotube arrays, and likely catalyst poisoning mechanisms responsible for the sharp decline in growth rates observed at high temperatures. PACS  61.46.+w; 81.07.De; 81.16.Hc     

Aligned growth and alignment mechanism of carbon nanotubes by hot filament chemical vapor deposition

Carbon nanotubes (CNTs) growth on Inconel sheets was carried out using hot filament chemical vapor deposition (HFCVD) in a gas mixture of methane and hydrogen. Scanning electron microscopy, transmission electron microscopy and field electron emission (FEE) measurement were applied to study the structure and FEE properties of the deposited CNTs. The effect of bias voltage and substrate surface roughness on the growth of vertically aligned carbon nanotubes was investigated. Well-aligned CNTs were synthesized by bias enhanced HFCVD. The results show that a bias of −500 V generates the best alignment. It has been observed that at the early growth stage, aligned and non-aligned CNTs are growing simultaneously on the unscratched sheets, whereas only aligned CNTs are growing on the scratched sheets. The results indicate that tip growth is not necessary for the electric field to align the CNTs, and larger catalyst particles created by scratching before the heat treatment can induce alignment of CNTs at the early growth stage. In addition, tree-like CNTs bundles grown on the scratched substrates exhibit better FEE performances than dense carbon nanotube forest grown on the unscratched substrates due to the reduced screen effect.     

Influence of the electric field on the alignment of carbon nanotubes during their growth and emission

The problems of the electric field action on carbon nanotubes (CNTs) during their growth and under the electron field emission conditions are considered. The relations determining the growth rate of an extended structure under the action of the electric field are established. The relation connecting the angle of orientation of a CNT inclined to the substrate surface and the applied electric field is used for computing current-voltage characteristics of the cathode consisting of inclined CNTs. The degree of deviation of these characteristics from the Fowler-Nordheim classic dependence is determined, on the one hand, by the parameters characterizing the CNT spread over the angles of inclination and, on the other hand, by the value of the Young modulus characterizing the bending stiffness of a nanotube. It is shown that in zero external electric field, a certain effect on the CNT orientation can be produced by the CNT potential relative to the substrate, which is due to the effect of the contact potential difference.     

碳纳米管薄膜场蒸发效应

在超高真空系统中对基于丝网印刷方法制备的碳纳米管薄膜的场蒸发效应进行实验研究. 实验发现, 碳纳米管薄膜样品存在场蒸发现象, 蒸发阈值场在10.0-12.6 V/nm之间, 蒸发离子流可以达到百皮安量级; 扫描电子显微镜分析和场致电子发射测量结果表明, 场蒸发会使碳纳米管分布变得更加不均匀, 会导致薄膜的场致电子发射开启电压上升(240→300V)、场增强因子下降(8300→4200)、蒸发阈值场上升(10→12.6V/nm), 同时使得薄膜场致电子发射的可重复性明显变好. 场蒸发也是薄膜自身电场一致性修复的表现, 这种修复并非表现在形貌上, 而是不同区域场增强因子之间的差距会越来越小, 这样薄膜场致电子发射的可重复性和稳定性自然会得到改善.     

Numerical study on the field emission properties of aligned carbon nanotubes using the hybrid field enhancement scheme

The magnitude of the local electric field and the electron emission current density for an array of aligned carbon nanotubes is estimated. For describing in detail the properties of the local electric field in the vicinity of the nanotube tips, a hybrid method allowing for the local determination of the field enhancement factor is introduced. The field factor consists of two parts: an internal factor which describes the structure of the carbon nanotubes and an external factor which represents the field screening effect due to neighboring nanotubes. The current density is obtained using the Fowler–Nordheim equation with the hybrid field enhancement scheme. As a result, the emission properties for an array of nanotubes with a given length are described satisfactorily, and an optimum value for the nanotube spacing is determined. PACS 85.45.Fd; 85.45.Db     

Influence of DC electric field on the Lennard-Jones potential and phonon vibrations of carbon nanotube on catalyst

Influence of DC electric field on carbon nanotube (CNT) growth in chemical vapor deposition is studied. Investigation of electric field effect in van der Waals interaction shows that increase in DC electric field raises the magnitude of attractive term of the Lennard-Jones potential. By using a theoretical model based on phonon vibrations of CNT on catalyst, it is shown that there is an optimum field for growth. Also it is observed that CNT under optimum electric field is longer than CNT in the absence of field. Finally, the relation between optimum DC electric field and type of catalyst is investigated and for some intervals of electric field, the best catalyst is introduced, which is very useful for experimental researches.     

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     

对碳纳米管阵列的场发射电场增强因子以及最佳阵列密度的研究

研究了外电场、碳纳米管自身线度、尤其管的阵列密度对碳纳米管的场发射性能的影响,从理论上深入探索碳纳米管阵列的电场增强因子并提出改善其场发射电子性能的有效途径.研究结果表明,碳纳米管阵列的电场增强因子的数量级一般为102—103,并对任何长径比的碳纳米管阵列,都对应着一个最佳阵列密度,当碳纳米管阵列密度取此最佳密度值时,其电场增强因子明显提高.这里的理论研究对弄清碳纳米管的场发射机理及实验合成高发射性能的碳纳米管阵列有一定的意义 关键词： 碳纳米管阵列 最佳阵列密度 电场增强因子 长径比     

Field emission of carbon nanotubes and electronic structure of carbon nanopeapods

We calculate the electron emission from nanostructures under an applied electric field using the ab initio pseudopotential method. The transition rates of the electrons are calculated by integrating the time-dependent Schrödinger equation for the states initially inside the emitter. A localized basis set is used for obtaining the eigenstates before emission and the potential that drives the field emission. The calculated electron-tunneling graph is quite linear in the short-time region, giving the transition rate within the simulation time. We have applied this new method to the field emission of carbon nanotubes as a test. Then we calculate the electronic structure of the fullerenes encapsulated inside the carbon nanotubes, the so-called carbon “nanopeapods”. The fullerenes may or may not contain metallic atoms such as gadolinium or potassium. There is an interesting effect of strain when the diameter of the carbon nanotube is smaller than that of the inserted fullerene plus twice the van der Waals distance.     

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.     

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 emission of electrons by carbon nanotube twist-yarns

Field emission with high current density at low operating voltage was found for the yarns obtained by solid state spinning process from forest of vertically aligned multiwall carbon nanotubes. The nanotube forest was produced catalytically by CVD method. It is found that only a small fraction of carbon nanotubes from their total amount in the yarn yields to electron emission from its free end. This led to resistive heating of the emitting tubes and limiting of the emission current. The field emission microscopy pictures of MWNT yarn in free-end geometry appears to be very different from that of the conventional non-yarn carbon nanotube-based cathodes described in all previous studies. The FEM patterns are found to consist of the set of line and arc segments rather than a set of spots. Possible explanation of this effect is presented and discussed. The field emission from the lateral side of the yarns showed the self-enhanced currents increasing with operation time. We assume that this current increase may be due to untwisting and unwrapping of yarns resulted of application of the electric field. The lowest threshold field of about 0.7 V/μm was obtained after a few cycles of applied field increase. The prototypes of cathodoluminescent lamps and alphanumerical indicators based on MWNT twist-yarn cold cathodes are demonstrated. PACS 79.70.+q; 61.46.Fg; 85.45.Db