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.     

Field emission characteristic of screen-printed carbon nanotube cathode

The fabrication of carbon nanotube emitters with excellent emission properties is described. The multi-walled carbon nanotubes (MWNTs) produced by chemical vapor deposition (CVD) method were purified with oxidation method and mixed with organic binding pastes and then screen-printed on glass substrates with ITO film. We applied anode voltage gradually to refine the emission behavior of the emitter by cleaning the top surface of screen-printed carbon nanotubes (CNTs). The density of the carbon nanotubes is about 2.5×10⁸/cm². Diode field emission experiments were performed in dynamic vacuum system to study the emission current, the emission uniformity, etc. Bright and stable character emission images were obtained in the diode structure and the emission current could approach 1 mA/cm².     

碳纳米管场致发射中的空间电荷效应

采用微波等离子体化学气相沉积(MWPCVD)方法成功制备以碳纳米管束为单元的场致发射阵列,获得很好的场致发射电流发射特性,在电流密度较大时,发现I-V特性偏离由Fowler-Nordheim公式计算出的结果。采用Electron Beam Simulation(EBS)软件进行模拟分析发现:在电流密度较低时,I-V特性能很好与F-N公式吻合。但碳纳米管尖端电流密度大于106A/cm2时,碳纳米管尖端处的有效电场强度受空间电荷的影响比较明显,进而对碳纳米管的场致发射特性显现出不可忽略的影响,此时碳纳米管的发射电流密度开始受到空间电荷的限制。     

Densities of states of low-index surfaces of tantalum by photofield emission

The total energy distributions (TED) of the true photofield emission current from clean (1 0 0), (1 1 0) and (1 1 1) facets of Ta field emitters have been measured using a new method to remove the thermocurrent associated with laser heating. Each TED exhibits one or more prominent peaks that are interpreted by comparing them with ab initio calculations of the TED of the emission current based on density functional theory. The generally good agreement with experiment indicates that the same method can be used for accurate calculations of the densities of states of low-index surfaces of Ta. Each of the experimental TEDs shows, in addition to the prominent peaks, a set of weaker peaks that are not predicted by the calculation and whose spacing depends on the sharpness of the field emitter. These weaker peaks are interpreted as arising from size-effect resonances in the microcrystal at the apex of the field emitter.     

Dissociation of carbon monoxide on stepped nickel surfaces

Field emission microscopy with photometric measurements has been applied to investigate the adsorption of carbon monoxide on various crystal planes of a nickel field emitter. Upon heating the CO-covered surface, the work function drastically decreased during desorption of CO molecules into the gas phase and exhibited almost the value of the clean surface at 450 K. However, part of the CO molecules adsorbed on the stepped planes such as (510) and (310) were found to dissociate upon heating at 450–470 K, which was accompanied by an increase of the work function of ～0.2 eV.     

基于碳纳米管场发射三电极显示器的设计和实验

提出了一种基于碳纳米管场发射三电极大面积全彩色平板显示器模型,其特点是栅极和阴极在同一个平面上,驱动电压低,而电子传输比可以高达29.3%(达到阳极的电子与从阴极碳管上发射出来的电子之比),实验结果和理论模拟的结果符合得很好.阴极和栅极之间的沟槽可以用激光打标机刻蚀形成,用做阴极发射体的碳纳米管浆料用水浴法形成,显示器制作工艺简单.     

Carbon nanotube field emission cathodes fabricated with trivalent chromium conversion coated substrates

The properties of carbon nanotube (CNT) field emission cathodes fabricated by a dip coating method with trivalent chromium conversion coated substrates are studied. Two kinds of substrates with different morphologies, one with a rough crackled surface and the other with a smooth surface, were used for making the CNT cathodes, and their I-V curves and emission patterns were evaluated. The results show that, as compared to the smooth substrate surface, the rough surface with self-assembled sub-micro-cracks on the substrate can dramatically enhance the uniformity of the emission pattern and the emission efficiency. The cathode fabricated with the crackled substrate shows good field emission properties such as high brightness, good uniformity, a low turn-on field (0.86 V/μm) and a high current density of 10 mA/cm² at 2.5 V/μm.     

The work function reduction of the Pt field emitter

We have carried out the field emission experiments to measure the temperature dependence of the work function of Pt field emitter and found that the work function steeply decreases more than 2 eV by annealing at relatively low temperature above about 500 K in ultra high vacuum. The maximum reduction of the work function was 2.59 eV. The reduced work function was restored the original value of Pt clean surface by applying high voltage of only 20% of Pt evaporation field. The experimental results are tentatively interpreted in terms of the formation of complex cyanides on the emitter shank during the electrochemical etching in KCN solution and the surface diffusion of potassium atoms formed by the thermal decomposition of the complex cyanides to the emitter cap.     

Effect of micro and nanoparticle inorganic fillers on the field emission characteristics of photosensitive carbon nanotube pastes

We successfully fabricated field emitter arrays of carbon nanotube (CNT) dots of 10 μm diameter with excellent field emission properties by using photosensitive CNT paste. The CNT paste was investigated in terms of morphologies, current-voltage properties, and luminous uniformities by varying the mixing ratios of micro and nanoparticle inorganic fillers and the amount of CNTs added into the paste. The 3:1 mixing of micro and nanoparticle fillers and the addition of 5% CNTs in the paste brought about the best field emission characteristics of dot-patterned CNT field emitter arrays.     

Modification of the tungsten carbide field emitter surface to localize the electron and ion emission

Using field emission microscopy, the shape modification of the tungsten carbide emitter simultaneously exposed to high electric fields and high temperatures is studied. It is shown that in this case the emitter shape changes observed on the emitter surface are the same as those observed in the pure metal emitters. The possibility to grow a single nanoprotrusion on the emitter surface which can emit charged particles with stability similar to that for the carbon material emitters is demonstrated. The values of the emission current, current density, emission angle, and reduced brightness are comparable to those for the carbon nanotube emitters, and the advantage of this single nanoprotrusion is its complete reproducibility and capability to emit not only electrons but also ions.     

Light emission from carbon nanofilaments/nanotubes at field electron emission

The spatial distribution of light emission has been studied in planar field electron emitters with long and sparse carbon nanofilaments/nanotubes. The photographic recording of light emission of the emitting nanofilaments/nanotubes is shown to be efficient to determine the position of individual nanofilaments/ nanotubes in different emitter surface areas, as well as to highlight the nanofilaments/nanotube agglomerate distribution over the emitter surface, which mainly contributes to its emission.     

Growth of multi-walled CNTs emitters on an oxygen-free copper substrate by chemical-vapor deposition

Field emission properties of carbon nanotubes directly grown on a well-polished oxygen-free copper substrate by chemical-vapor deposition (CVD) were studied. Ni was sputtered on the copper substrate as catalyst, and the reactant gas was acetylene. From scanning electron microscopic and transmission electron microscopic images, the as-grown carbon nanotubes are seen to be bamboo structure with branches. Efficient field emission of CNTs is measured by a diode configuration, and the maximum current is 4.8 mA corresponding to a low electric field of 6.7 V/μm (the emission area is about 3.14 mm²). The diffusion between nickel and copper substrate is found to cause the loss of catalyst based on X-ray diffraction pattern of the surface of the substrate.     

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.     

Enhanced electron field emission characteristics of single-walled carbon nanotube films by ultrasonic bonding

A novel ultrasonic bonding process was used to fabricate the electron field emission cathode of single-walled nanotube film, which was deposited on an Al plate substrate by electrophoretic deposition. Electron field emission properties were improved remarkably after the cathode carbon nanotubes nanobonded with the Al substrate. Turn-on voltage showed a significant decrease and the emission current was much stabilized. This can be attributed to the reduction of the contact resistance in bonding area and easily moving electrons for field emission after ultrasonic bonding. In addition, the field emission performances of SWCNTs films formed at different bonding conditions were also studied. With a simple nano-bonding apparatus, this technique has low cost, and can be utilized for extensively roboticized fabrication of high performance field emission cathodes with short process time.     

封装钠的硼氮纳米管在垂直构型下场发射的第一性原理研究

采用密度泛函形式化的自洽方法模拟了纯的硼氮纳米管和封装钠的硼氮纳米管在垂直于管轴的电场作用下的场发射. 发现硼氮纳米管封装钠之后的近自由电子态参与场发射并表现出很强的发射特性.通过分析场发射总能量分布曲线的特征,探索近自由电子态对于场发射的作用和场发射电流对于外电场的响应. 发现在垂直管轴的发射构型下,场发射具有很灵敏的电场响应度,这是与硼氮纳米管中近自由电子态的特殊分布取向有关.     

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.     

Field emission energy distribution (clean surfaces)

The emission of electrons from a cold cathode upon application of a strong electric field is called field emission. Since the electrons must tunnel through the classically forbidden barrier outside the solid, field emission was one of the first confirmations of the new quantum theory of the 1920's.¹ A field of tens of million volts per centimeter is required to obtain a reasonable current. In order to achieve such hgh fields at reasonable voltages, the cathode or emitter is usually etched to a very sharp point (～1,000 Å in radius). Therefore, several thousands of volts applied to the anode will produce the desired field. In 1937, Miiller2 developed what is known as the field emission microscope. The success of Miiller's microscope was a consequence of his realization that, if he produced a small hemispherically shaped tip that was thermally smoothed and cleaned, he would project a greatly magnified image of the spatial distribution of electrons tunneling from the emitter onto a fluorescent screen. Such a field emission pattern for clean tungsten is shown in Figure 1. The image on the screen is a nearly stereographic projection of the hemispherical end of the emitter. Because of its small size, the emitter is usually part of a single crystal and thus exposes all crystallographic orientations, so that individual crystal planes can be located and identified in the field emission pattern. The changes in the field emission pattern with exposure to adsorbed atoms or molecules have been used very successfully to study surface processes, such as diffusion, adsorption and desorption kinetics, or work function changes.³     

Enhanced field emission from LaB6 thin films with nanoprotrusions grown by pulsed laser deposition on Zr foil

Lanthanum hexaboride (LaB₆) films have been deposited on a zirconium foil by pulsed laser deposition method. The field emission studies of the LaB₆ deposited film have been performed in the planar diode configuration under ultra high vacuum conditions. The Fowler-Nordheim plots were found to be linear in accordance with the quantum mechanical tunneling phenomenon. A typical field emission current of 7.02 μA was drawn at an applied electric field of 2 V/μm. The field enhancement factor is calculated to be 8913 cm⁻¹, indicating that the field emission is from nanoscale protrusions present on the emitter surface. The atomic force microscope (AFM) investigation of the surface clearly shows the conical shaped nanoprotrusions of few hundred nanometers with asperities of 20-40 nm on its top. The emission current-time plot recorded at the pre-set value of emission current of 5 μA over a period of more than 3 h exhibits an initial increase and subsequent stabilization of the current. The results reveal that the LaB₆/Zr field emitter obtained by the pulsed laser deposition (PLD) is a promising cathode material for practical applications in field emission-based devices.     

利用场发射显微镜研究O2对单壁碳纳米管场发射的影响

利用场发射显微镜和四极质谱计研究了充入高纯O2的四极质谱和O2对单壁碳纳米管场发射的影响.单壁碳纳米管经过约1000℃的热处理得到清洁态场发射像后，充入O2，分别测量了O2吸附和脱附后场发射的I V特性.实验观测到在单壁碳纳米管上O2的吸附使场发射电流减小，说明逸出功增加.在10-4Pa的O2压强下对单壁碳纳米管进行约1000℃的热处理，可以产生氧化刻蚀作用，观测到场发射像的变化，并测量了氧化刻蚀产生的I V特性变化. 关键词： 单壁碳纳米管 场发射显微镜 场发射 四极质谱     

Field emission from self-assembly structure of carbon-nanotube films

Chemical vapor deposited (CVD) carbon nanotube (CNT) arrays were immersed in ethanol to make shrunk structures with separate nanotube “walls” for better field emission properties, such structures decreased the screening effects and reduced the turn-on electric field at 10 μA/cm² from 1.68 to 1.23 V/μm. The field enhancement factor was calculated to increase by 23% according to Fowler–Nordheim (F–N) equation. The number of emission sites also increased and their distribution was more uniform.