激光烧蚀对碳纳米管薄膜场发射性能的影响

采用丝网印刷工艺制作了碳纳米管(CNTs)薄膜阴极.经适当能量激光烧蚀后,相互粘连的CNTs随表面粘附有机物的蒸发而分散开,管间隙增加、屏蔽效应减小,使得场发射性能大幅度提高,开启场强降低、场倍增因子β增大.Raman光谱分析表明,随激光能量增加,CNTs表面缺陷增多,成为新的场发射点,对其β增大的贡献加强.相对于两电极结构,三电极中平栅极结构场发射性能经激光烧蚀有更显著的改善.这说明激光烧蚀是提高CNTs场发射性能的有效方法. 关键词： 碳纳米管薄膜 场发射 激光烧蚀 Raman光谱     

Improved emission uniformity and stability of printed carbon nanotubes in electrolyte

In this paper, we studied the effect of NaCl electrolyte as a surface treatment on improving the uniformity and stability of field emission of screen-printed carbon nanotubes (CNTs). A short period of the electrolyte treatment of CNT films remarkably increase emission uniformity and stability. Furthermore, the field emission characteristics of screen-printed carbon nanotubes (CNTs) such as low turn-on field, high emission current density and strong adhesion of the CNT film on the substrate were also reinforced after post-treated. SEM, TEM and Raman spectrum study revealed that uniformity and stability of field emission is enhanced by two factors. Firstly, the electrolyte treatment appeared to render the CNT surfaces more actively by exposing more CNTs form the CNT paste, which dominates initial uniformity and stability of field emission. Secondly, the number of opened CNTs and defects CNTs of CNT film were increased by electrical current energy.     

Enhanced field emission characteristics of zinc oxide mixed carbon nano-tubes films

A composite material of Zinc oxide and carbon nano-tubes (ZnO-CNTs) paste was synthesized by mixing multi-wall CNTs, ZnO nano-grains and organic vehicles. The microstructures and the morphologies of screen-printed films were characterized by field-emission scanning electron microscope. Results show that ZnO flakes geometrically matched with CNTs by filling into the interspaces of CNTs or directly covering upon CNTs. The field emission characteristics of films are found to be greatly effected by ZnO nano-grains. Especially, the turn-on electric field of ZnO-CNT film (1.17 V/μm) which is far lower than that of usual CNT films (1.70 V/μm). Furthermore, except that better emission stability is achieved, brightness and emission uniformity are notably enhanced as well. It can be speculated that the special microstructures of ZnO mixed CNT films dominate the enhanced electrical conductivity, thermal conductivity, and effective emitters.     

Effect of sputtered Cu film’s diffusion barrier on the growth and field emission properties of carbon nanotubes by chemical vapor deposition

Growth of carbon nanotube (CNT) films with good field emission properties on glass is very important for low cost field emission display (FED) applications. In addition to Ni, Co and Fe, Cu can be a good catalyst for CNT growth on glass, but due to diffusion into SiO₂ it is difficult to control the CNTs density and uniformity. In this paper, four metal barrier layers (W, Ni, Cr, Ti) were deposited by dc magnetron sputtering on glass to reduce the Cu diffusion. As-grown CNT films showed various morphologies with the use of different barrier metals. CNTs with uniform distribution and better crystallinity can be synthesized only on Ti/Cu and W/Cu. Voltage current measurements indicate that better field emission properties of CNT films can be obtained on titanium and tungsten barriered Cu, while chromium and nickel are not suitable barrier candidates for copper in CNT-FED applications because of the reduced emission performance. PACS 81.05.Uw; 61.46.Fg; 85.45.Db; 66.30.-h     

Effects of microwave plasma treatment on the field emission properties of printed carbon nanotubes/Ag nano-particles films

The effects of Ar microwave plasma treatment on field emission properties of the printed carbon nanotubes (CNTs) cathode films using Ag nano-particles as binder were investigated. The field emission J-E characteristics were measured at varied plasma treatment time. Significant improvement in emission current density, emission stability and uniformity were achieved for the Ar treated CNTs films, even though the plasma treatment increased the turn on electric field slightly. High-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy revealed the microstructural changes of CNTs after the plasma treatment. The improved field emission properties of CNTs film can be attributed to the generation of a high density of structural defects after treatment, which increased greatly the possible emission active sites. Besides, the formation of the sharpened and open-ended CNTs tips is all helpful for improving the field emission properties of the treated CNTs.     

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.     

Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

Electron field emission properties of highly dense carbon nanotube arrays

In this paper, we have studied field emission properties of highly dense arrays of multi-walled carbon nanotubes (CNTs) used as cathodes in diode-type field emission devices with a phosphor screen. For the high-density CNT emitters it is demonstrated that the emission sites are located on the CNT-cathode edges, which is direct experimental evidence of the ‘edge effect’. The results of computer simulations (using ‘ANSYS Electromagnetic’ software) are presented to confirm the experimental data and to analyze the effect of patterning on the electric field distribution for high-density CNT arrays. It is shown that selective-area removal of nanotubes in the arrays leads to the formation of additional edges characterized by the high field enhancement factor and enhanced emission from the CNT cathodes. In addition, scanning probe microscopy techniques are employed to examine surface properties of the high-density CNT arrays. For CNT arrays of ‘short’ nanotubes, the work function distribution over the sample surface is detected using a scanning Kelvin microscopy method.     

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.     

沉积工艺参数对碳纳米管薄膜场发射性能的影响

利用微波等离子体化学气相沉积(MWPCVD)方法,在不锈钢衬底上直接沉积碳纳米管膜。通过SEM、拉曼光谱和XRD表征,讨论了制备温度和甲烷浓度对碳纳米管膜场发射的影响。结果表明:不同条件下制备的碳纳米管膜的场发射性能有很大差异,保持氢气的流量(100sccm)、生长时间(10min)、反应室压力不变,当甲烷流量为8sccm、温度为700~800℃时,场发射性能最好,开启场强仅为0.8V/μm,发射点分布密集、均匀。     

场致发射阴极碳纳米管的热化学气相沉积法低温生长

结合丝网印刷和过滤阴极真空电弧法、离子束溅射方法，在普通玻璃衬底上制备催化剂图案，采用低温热化学气相沉积法(CVD)生长碳纳米管/纤维(CNTs)薄膜.研究了不同种类催化剂对CNTs薄膜生长及其场发射的影响.结果表明，在a-C:Co,Ni-Cu和Cu三种催化剂上没有获得明显的CNTs，在外加电场小于4.4V/μm时没有观察到场发射；而在Ni-Fe及Ni-Cr两种催化剂上获得了大量的CNTs，并且表现出良好的场发射性能，开启电场为2.5V/μm，这种热CVD有简单、低温等优点，在CNTs场发射显示器的阴极制备中有潜在的应用价值.     

Characterization and field-emission property of aligned porous carbon nanotube film by hydrogen-ion implantation

To enhance the field emission of carbon nanotube (CNT) films, a novel technique that combines hydrogen-ion implantation used in the silicon-on-insulation smart-cut process and plasma-enhanced chemical vapor deposition was developed to produce an aligned porous carbon nanotube (AP-CNT) film on a Si substrate. All steps in the AP-CNT synthesis were carried out in vacuum, which reduced possible contamination. The morphology and the field-emission properties of the CNT films were investigated and results show that CNT holes with a diameter of 5 m and a depth of 30 m were produced in the AP-CNT film. The alignment of the CNTs is visibly improved. Due to the implantation treatment, the turn-on field of the CNT films decreased from 1.5 to 0.8 V/m, and the emission-current (and dot) density obviously increased. This field-emission improvement may mainly arise from the holes formed in the AP-CNT films. The edges of these holes not only intensified the electron emission but also increase the emission site density of the CNT films. PACS 81.05.Uw; 61.72.Tt; 85.45.Db     

离子束辐照的碳纳米管及其物性研究

离子束辐照通常被认为导致材料产生缺陷, 形成无序结构, 从而破坏材料的性能。 但是, 最近利用离子束辐照碳纳米管的实验显示离子束辐照碳纳米管形成无定形的过程不能用传统的离子束辐照材料的机制来解释, 离子束辐照可导致碳纳米管形成一些自组装结构, 如无定形碳纳米结和碳纳米管连接结等。 研究还发现离子束辐照的碳纳米管薄膜在导电性和场发射性能方面都能得到明显的增强。 Ion beam irradiation is usually thought to induce defects and disordered structures in materials and then to destroy the properties of the materials. However, our recent experiments about the ion beam irradiation on carbon nanotubes(CNTs) indicate that the ion beam modification mechanism of CNTs is completely different from traditional one of bulk materials, and ion beam irradiation can lead to self organized structures in CNTs, such as amorphous junctions and CNT junctions. Moreover, the irradiated CNTs exhibit a improved conductivity and an enhanced field emission.     

Influence of field evaporation treatment on the field emission properties of carbon nanotubes array

Field evaporation was used in the post-fabrication treatment of a carbon nanotubes (CNTs) array and effectively modified the CNTs morphology in favor of the field emission under a moderate field. After the field evaporation treatment, the uniformity of the emission site distribution improved but the onset voltage rose. Using the Fowler-Nordheim theory, the actual onset field and the evaporation field around the CNT were calculated to be −4.6-5 and 9-12 V/nm, respectively. These values are close to those obtained from the individual CNT samples. The above results have provided an alternative to modify the configuration of an array sample and demonstrated the feasibility of tackling the problem of the disparity in the field emission capability of different CNTs in an array.     

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.     

Field emission properties of carbon nanotube cathodes produced using composite plating

Field emission properties of carbon nanotube field emission cathodes (CNT-FECs) produced using composite plating are studied. The experiment uses a CNT suspension and electroless Ni plating bath to carry out composite plating. The CNTs were first purified by an acid solution, dispersed in a Ni electrobath, and finally co-deposited with Ni on glass substrates to synthesize electrically conductive films. Field emission scanning electron microscopy and Raman spectroscopy results show that the field emission characteristics and graphitic properties of CNT-FECs depend on the pH value of the electrobath. Experiments show that the optimum electrobath pH value is 5.4, achieving a field emission current density of 1.0 mA/cm² at an applied electric field of 1.5 V/μm. The proposed CNT-FECs possess good field emission characteristics and have potential for backlight unit application in liquid crystal displays.     

Field emission characteristics of carbon nanotubes post-treated with high-density Ar plasma

The field emission characteristics of carbon nanotubes (CNTs) grown by thermal chemical vapor deposition (CVD) and subsequently surface treated by high-density Ar plasma in an inductively coupled plasma reactive ion etching (ICP-RIE) with the various plasma powers were measured. Results indicate that, after treated by Ar plasma with power between 250 and 500 W, the emission current density of the CNTs is enhanced by nearly two orders of magnitude (increased from 0.65 to 48 mA/cm²) as compared to that of the as-grown ones. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the structural features relevant to the modified field emission properties of CNTs. The SEM images of CNTs subjected to a 500 W Ar plasma treatment exhibit obvious damages to the CNTs. Nevertheless, the turn-on fields decreased from 3.6 to 2.2 V/μm, indicating a remarkable field emission enhancement. Our results further suggest that the primary effect of Ar plasma treatment might be to modify the geometrical structures of the local emission region in CNTs. In any case, the Ar plasma treatment appears to be an efficient method to enhance the site density for electron emission and, hence markedly improving the electric characteristics of the CNTs.     

Modeling and simulation for the field emission of carbon nanotubes array

To optimize the field emission of the infinite carbon nanotubes (CNTs) array on a planar cathode surface, the numerical simulation for the behavior of field emission with finite difference method was proposed. By solving the Laplace equation with computer, the influence of the intertube distance, the anode–cathode distance and the opened/capped CNT on the field emission of CNTs array were taken into account, and the results could accord well with the experiments. The simulated results proved that the field enhancement factor of individual CNT is largest, but the emission current density is little. Due to the enhanced screening of the electric field, the enhancement factor of CNTs array decreases with decreasing the intertube distance. From the simulation the field emission can be optimized when the intertube distance is close to the tube height. The anode–cathode distance hardly influences the field enhancement factor of CNTs array, but can low the threshold voltage by decreasing the anode–cathode distance. Finally, the distribution of potential of the capped CNTs array and the opened CNTs array was simulated, which the results showed that the distribution of potential can be influenced to some extent by the anode–cathode distance, especially at the apex of the capped CNTs array and the brim of the opened CNTs array. The opened CNTs array has larger field enhancement factor and can emit more current than the capped one.     

A comparative study of field emission properties of carbon nanotube films prepared by vacuum filtration and screen-printing

A comprehensive comparative study of electron field emission properties of carbon nanotube (CNT) films prepared by vacuum filtration and screen-printing was carried out. Field emission performance of vacuum filtered CNT films with different filtered CNT suspension volumes was systematically studied, and the optimum electron emission was obtained with a low turn on field of ∼0.93 V/μm (at 1 μA/cm²) and a high field enhancement factor β of ∼9720. Comparing with screen-printed CNT films, vacuum filtered CNT films showed better electron emission performance, longer lifetime, and greater adhesive strength to substrates. This work reveals a potential use of vacuum filtered CNT films as field emission cathodes.     

高能球磨对碳纳米管形貌及场致发射显示特性的影响

用化学气相沉积法制备了碳纳米管,进行了不同时间的球磨处理。用扫描电镜、拉曼光谱对其形貌和结构进行了表征。对不同球磨条件下的碳纳米管制备成阴极,进行了场致发射特性的测试。结果表明,高能球磨会对碳纳米管的形貌、结构及场致发射性能有明显的影响。球磨时间为0．5～1h时,可以使碳纳半管变短而均匀,且场致发射电性能与未处理时相近,即有低的阈值电场和高的发射电流密度,从而使发射时在阳极上产生的荧光点密度大大增加,发光均匀。但研磨时间过长会改变碳纳半管结构,使其非晶化或石墨化,导致其场致发射性能和显示效果变差。