Field emission from a selected multiwall carbon nanotube

The electron field emission characteristics of individual multiwalled carbon nanotubes were investigated by a piezoelectric nanomanipulation system operating inside a scanning electron microscopy chamber. The experimental set-up ensures a precise evaluation of the geometric parameters (multiwalled carbon nanotube length and diameter and anode-cathode separation) of the field emission system. For several multiwalled carbon nanotubes, reproducible and quite stable emission current behaviour was obtained, with a dependence on the applied voltage well described by a series resistance modified Fowler-Nordheim model. A turn-on field of ～30?V?μm(-1) and a field enhancement factor of around 100 at a cathode-anode distance of the order of 1?μm were evaluated. Finally, the effect of selective electron beam irradiation on the nanotube field emission capabilities was extensively investigated.     

Formation of free-standing carbon nanotube array on super-aligned carbon nanotube film and its field emission properties

Flexible and free-standing well-aligned carbon nanotube arrays have been synthesized on super-aligned carbon nanotube films. The combined structure of the carbon nanotube array and carbon nanotube film was formed during chemical vapor deposition on a quartz substrate which had previously been covered with a super-aligned carbon nanotube film. It was found that the growing carbon nanotube array could support up the super-aligned carbon nanotube film entirely, and the top of the array became densely entangled with the super-aligned carbon nanotube film. The carbon nanotube array with the super-aligned carbon nanotube film could be easily peeled off from the quartz substrate as a whole, giving a flexible and free-standing structure with good mechanical properties. The bottom of the array was also exposed after being peeled off and was used as a field emitter. The combined structure of the carbon nanotube array with the carbon nanotube film allowed adsorbent-free field emission by passing a heating current through it. Furthermore, due to the fast thermal response of the structure and the long time needed for re-adsorption of adsorbates in vacuum, it was found that pulsed heating with a 10% duty ratio was sufficient for adsorbent-free field emission. The heating power necessary to sustain the adsorbent-free state can be lowered in this way.

Open image in new window

     

Field emission properties of carbon nanotube arrays on the thickness-controlled flexible substrate by the pattern transfer process

A technigal with the polydimethylsiloxane (PDMS) solution infiltrated into the SiOx-coated CNTAs has been utilized to directly transfer the CNTAs away from the silicon substrate. The oxide coating layer was utilized to protect the morpholgy of as-grown patterned vertical aligmed carbon nanotube (CNTs) arrays. The high density plasma reactive ions etching (HDP-RIE) system was used to make the CNTs emerge from the surface of the flexible substrate and modify the crystallines of CNTs. After the protecting oxide was HDP-RIE-processed for 8 min, the emission current properties were enhanced to be 1.03 V/microm and 1.43 V/microm, respectively, for the turn-on field and the threshold field, as compared with 1.25 V/microm and 1.59 V/microm for the as-grown CNTs, accordingly. The Field Emission (FE) enhancement after dry etching could be attributed to the open-ended structures and better crystalline.     

Field emission and lifetime characteristics of carbon nanotube paste including nitrogen-foaming agent

Azodicarbamide (ADCA) was added to carbon nanotube (CNT) paste to protect it from degradation. This agent produces nitrogen gas (N₂) by heating at 190–210 °C, which acts as the anti-oxidant for carbon nanotube paste. The measurements of field emission and lifetime were evaluated in a vacuum chamber with a diode structure with pulsed current (duty of 1/500) mode; the lifetime of protected carbon nanotube samples was about five times greater than that of the pristine ones.     

Enhanced field emission properties of vertically aligned double-walled carbon nanotube arrays

Vertically aligned double-walled carbon nanotube (VA-DWCNT) arrays were synthesized by point-arc microwave plasma chemical vapor deposition on Cr/n-Si and SiO(2)/n-Si substrates. The outer tube diameters of VA-DWCNTs are in the range of 2.5-3.8?nm, and the average interlayer spacing is approximately 0.42?nm. The field emission properties of these VA-DWCNTs were studied. It was found that a VA-DWCNT array grown on a Cr/n-Si substrate had better field emission properties as compared with a VA-DWCNT array grown on a SiO(2)/n-Si substrate and randomly oriented DWCNTs, showing a turn-on field of about 0.85?V?μm(-1) at the emission current density of 0.1?μA?cm(-2) and a threshold field of 1.67?V?μm(-1) at the emission current density of 1.0?mA?cm(-2). The better field emission performance of the VA-DWCNT array was mainly attributed to the vertical alignment of DWCNTs on the Cr/n-Si substrate and the low contact resistance between CNTs and the Cr/n-Si substrate.     

Catalyst design for carbon nanotube growth using atomistic modeling

The formation and stability of bimetallic catalyst particles, in the framework of carbon nanotube growth, is studied using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Monte Carlo-Metropolis simulations with the BFS method are utilized in order to predict and study equilibrium configurations for nanoscale catalyst particles which are directly relevant to the catalyst state prior to growth of carbon nanotubes. At the forefront of possible catalyst combinations is the popular Fe-Mo bimetallic catalyst, which we have recently studied experimentally. We explain our experimental results, which indicate that the growth observed is dependent on the order of co-catalyst deposition, in the straightforward interpretation of BFS strain and chemical energy contributions toward the formation of Fe-Mo catalyst prior to growth. We find that the competition between the formation of metastable inner Mo cores and clusters of surface-segregated Mo atoms in Fe-Mo catalyst particles influences catalyst formation, and we investigate the role of Mo concentration and catalyst particle size in this process. Finally, we apply the same modeling approach to other prominent bimetallic catalysts and suggest that this technique can be a powerful tool to understand and manipulate catalyst design for highly efficient carbon nanotube growth.     

Field emission properties of metallic element-containing glassy carbon films

Field emission properties of metallic element-containing glassy carbon (GC) films were investigated. The metallic element-containing GC films were prepared by carbonization process (i.e., heat treatment in an inert atmosphere) of synthesized polyimide including a metallic compound. In the alkaline (lithium(Li) or cesium(Cs)) or alkali-earth (calcium(Ca), strontium(Sr), or barium(Ba)) metallic element-containing GC films, threshold electric field, E_th, decreased and emission current density, J, increased. In particular, as for the Ba-containing GC film, E_th was decreased to 1.5 V/μm compared with E_th of 3.5 V/μm for the pure GC film without the metallic element addition, and the J reached more than 0.8 mA/cm² at an electric field of 3.0 V/μm. Analysis based on the Fowler-Nordheim model suggests that the amplification of the local-field-conversion factor β and/or the lowering of the effective-surface-potential barrier ? are due to the metallic elements contained in the GC films. Moreover, structural and compositional analyses showed that compositional modification of the GC film by the metallic elements plays an important role in allowing easy field emission.     

蒸镀碳化铪(HfC)对单根碳纳米管场致发射性能的改善

采用双向电泳法,在原子力显微镜探针尖端组装了单根碳纳米管,在真空环境下对比测量了单根碳纳米管蒸镀低逸出功材料HfC前后场致发射电流曲线和电流噪声的特点。证明了HfC蒸镀在碳纳米管上能够显著降低发射体的逸出功,减少电流噪声,并且观察到单根碳纳米管蒸镀了HfC后7μA左右的稳定电流发射。通过分析电流噪声,认为碳纳米管场致发射噪声主要来自吸附气体的频繁吸附和脱附。在低电流下,空间电离的离子轰击发射体表面,对吸附状态的影响占主导地位。当单根碳纳米管的场致发射电流超过1μA量级以后,碳纳米管表面温度快速升高,温度对气体吸附的影响占主导地位,吸附的气体分子逐渐脱附后,电流噪声开始降低。     

Tunable field emission properties of carbon nanotube arrays by engineering Fe catalysts

High-quality carbon nanotube (CNT) arrays composed of nanotubes with different diameters and wall numbers were synthesized by water-assisted chemical vapor deposition (CVD) from engineered Fe catalysts. Interestingly, the distribution of nanotube diameter and wall number broadened over 2.5 times as the catalytic Fe thickness increased. The mean diameter and wall number of nanotubes increased monotonically with the Fe thickness, while the calculated CNT area density within an array dropped about 32 times. Field emission measurements revealed that the turn-on voltage for CNT arrays decreased from 3.5 to 2.5 V/µm with the increased catalytic Fe thickness. It was believed that the screening effect from the proximity of neighboring nanotubes has a dominant influence than the CNT diameter on the resulting turn-on voltage.     

Field emission properties of carbon nanotubes with different morphologies

The field emission behavior of base-model well-aligned carbon nanotubes (Base-CNTs), curled carbon nanotubes (Curled-CNTs), and tip-model well-aligned CNTs (Tip-CNTs) was examined. The nanotubes were fabricated by means of direct current plasma-enhanced chemical vapor deposition using different ammonia (NH₃) pre-treatment plasma currents. The turn-on electric field values required to obtain a 10-nA current for Base-CNTs, Curled-CNTs, and Tip-CNTs were determined at 3.8, 4.3, and 4.9 V/μm, respectively. The field enhancement factor γ of Base-CNTs, calculated from a Fowler–Nordheim plot, was higher than that for the Curled-CNTs and Tip-CNTs. In the presence of a strong electric field, argon ion irradiation permanently straightened the as-grown Curled-CNTs films. The straightening process enhanced the emission properties of the as-grown Curled-CNTs films by decreasing the turn-on field and increasing the total emission current. Thus, morphology parameters of the MWNTs significantly affect the emission properties of CNTs.     

Field emission characteristics of an individual carbon nanotube inside a field emission-scanning electron microscope

Field emission (FE) properties of individual single-walled carbon nanotubes (SWCNT) were investigated inside a field emission-scanning electron microscopy. The individual SWCNT turned on a voltage of 23 V defined to produce a current of 10 pA, and was saturated at around 43 V and 880 nA. The FE characteristic of individual SWCNT also followed a conventional Fowler-Nordheim (F-N) theory in which a single linear slope in the F-N plots is measured below their limit of current level corresponding to the saturation regime of emission current. Energy-dispersive X-ray spectroscopy analysis showed that carbon atoms were deposited on the anode surface by the local heating of SWCNT tip during the FE processes and indicated about atomic 83% of carbon atoms. The carbon atoms were newly found to be evaporated and deposited on the anode surface during the FE process such that it was assumed that the degradation of FE was caused by evaporation and deposition of carbon atoms during the FE process.     

衬底电极对丝网印刷CNT阴极场发射性能的影响

通过丝网印刷技术,将碳纳米管(carbon nanotube,CNT)浆料直接转移到CrCuCr薄膜衬底电极、掺Sn的In_2O_3(indium tin oxides,ITO)透明导电薄膜衬底电极和Ag浆导电厚膜衬底电极上,高温烧结后得到CNT阴极,并对CNT阴极进行表面形貌和场发射性能的研究.结果表明,不同衬底电极对CNT阴极场发射性能的影响不一样,CrCuCr薄膜衬底电极CNT阴极、ITO透明导电薄膜衬底电极CNT阴极及Ag浆厚膜导电衬底电极CNT阴极场发射的开启电场分别为0.99、2.05和2.46V/μm;当电场为3.0V/μm时,它们的亮度分别为2472、1889、587cd/m~2.CrCuCr薄膜衬底电极CNT阴极的场发射性能最优,ITO透明导电薄膜衬底电极CNT阴极次之,Ag浆厚膜导电衬底电极CNT阴极最差,并根据金属-半导体理论模型分析了原因.     

Field emission properties of carbon nanotubes coated with boron nitride

Field emission properties of carbon nanotubes coated with a single layer of boron nitride are calculated using the first-principles pseudopotential method. At lower bias voltage, the emission current of the coated nanotube is comparable to that of the bare carbon nanotube and is dominated by the contribution from localized states at the tip of the tube. At higher voltage, newly generated hybridized states between the carbon nanotube tip and the even-membered boron nitride rings contribute significantly to the emission current because they experience a low tunneling barrier compared with the bare carbon nanotube case. Our results suggest that the insulator coating can, besides protecting the nanotube tip from the attack of gas molecules, substantially enhance the field emission current.     

Emitter spacing effects on field emission properties of laser-treated single-walled carbon nanotube buckypapers

Carbon nanotube (CNT) emitters on buckypaper were activated by laser treatment and their field emission properties were investigated. The pristine buckypapers and CNT emitters' height, diameter, and spacing were characterized through optical analysis. The emitter spacing directly impacted the emission results when the laser power and treatment times were fixed. The increasing emitter density increased the enhanced field emission current and luminance. However, a continuous and excessive increase of emitter density with spacing reduction generated the screening effect. As a result, the extended screening effect from the smaller spacing eventually crippled the field emission effectiveness. Luminance intensity and uniformity of field emission suggest that the highly effective buckypaper will have a density of 2500 emission spots cm(-2), which presents an effective field enhancement factor of 3721 and a moderated screening effect of 0.005. Proper laser treatment is an effective post-treatment process for optimizing field emission, luminance, and durability performance for buckypaper cold cathodes.     

碳纳米管场发射电子源

从实验和理论上研究单根碳纳米管(CNT)场发射电子源的稳定问题.利用透射电镜/扫描探针显微镜(TEM/SPM)和场发射显微镜/场离子显微镜(FEM/FIM)对CNTs的场发射特性进行了实验研究.同时从密度泛函理论出发,利用相关程序模拟计算了吸附对单壁碳纳米管(SWNTs)场发射的影响.发现SWNTs荷电体系的总能量与荷电电荷数量关系具有抛物线形式,先减小,达到最小值,之后增加.通常荷4个电子时达到最小值,即体系处于最稳定状态.表明SWNTs有很大的电负性,是容易发生凝聚和吸附分子的根源.进而计算了对氢、氧和水的吸附特性,讨论了吸附对场发射的影响.这些结果对CNTs的场发射特性和作为新型电子源的应用都是有重要意义的.     

Conceptual design of carbon nanotube processes

Carbon nanotubes, discovered in 1991, are a new form of pure carbon that is perfectly straight tubules with diameter in nanometers, length in microns. The conceptual designs of two processes are described for the industrial-scale production of carbon nanotubes that are based on available laboratory synthesis techniques and purification methods. Two laboratory-scale catalytic chemical vapor deposition reactors were selected for the conceptual design. One (CNT-PFR process) used the high-pressure carbon monoxide disproportionation reaction over iron catalytic particle clusters (HiPCO reactor), and the other (CNT-FBR process) used catalytic disproportionation of carbon monoxide over a silica supported cobalt–molybdenum catalyst (CoMoCAT reactor). Purification of the carbon nanotube product used a multi-step approach: oxidation, acid treatment, filtration and drying. Profitability analysis showed that both process designs were economically feasible. For the CNT-PFR process, the net present value, based on a minimum attractive rate of return of 25% and an economic life of 10 years, was $609 million, the rate of return was 37.4% and the economic price was $38 per kg of carbon nanotube. For the CNT-FBR process, the net present value was $753 million, rate of return was 48.2% and the economic price was $25 per kg of carbon nanotube. The economic price for these processes is an order of magnitude less than the prevalent market price of carbon nanotubes and is comparable to the price of carbon fibers.     

双掺杂碳纳米管电子场发射性能的密度泛函研究

采用第一性原理的密度泛函理论(DFT)研究了(5,5)碳纳米管(CNT)顶端硼(B)、氮(N)、硅(Si)等元素双掺杂体系的电子场发射性能.结果表明,在外电场下,各种双掺杂CNT帽端态密度(DOS)向价带移动.电子轨道分布变化显著,电荷分布明显局城化.根据电子态密度、差分电荷密度、最高分子占据轨道(HOMO)/最低分子非占据轨道(LUMO)分布等计算结果可预期Si双掺杂后更有利于场致电子发射.     

Effect of nano-silver particles in bonding material on field emission properties for carbon nanotube cathodes

Effects of bonding materials in a screen-printing paste on field emission properties were investigated for carbon nanotube (CNT) cathodes. The CNT cathodes were characterized for their dependence on current density in terms of the sintering behavior of the bonding material. As the diameter of the Ag particles in the bonding material decreased from 1000 nm to 10 nm, the current density of the CNT cathode increased. The sintering temperature of bonding materials was decreased for small silver (Ag) particles in bonding material. The higher current density for a CNT cathode fabricated with smaller Ag particles was primarily due to the lower sheet resistance of the bonding material after heat treatment.     

Field emission properties of Fe70Pt30 catalysed multiwalled carbon nanotubes

Multi-walled carbon nanotubes were grown on nanocrystalline Fe₇₀Pt₃₀ film using low-pressure chemical vapour deposition (LPCVD) method. The growth time was varied between 5?min to 30?min. SEM micrograph of this film revealed that the size of nanoparticles varied from 5?nm to 10?nm. The diameter of the carbon nanotubes varied from 20?nm to 50?nm as verified by TEM. HRTEM image confirmed that the carbon nanotubes are bamboo-shaped multiwalled carbon nanotubes (MWNTs). Field emission characteristics of MWNTs at various growth times (5?min, 15?min and 30?min) with working distances (50?µm, 100?µm and 150?µm) were also studied. The carbon nanotubes grown for 30?min with working distance 150?µm exhibited the lowest turn-on field of 2.45?V/µm. The turn-on field increases from 2.45?V/µm to 6.21?V/µm as the growth time decreases from 30?min to 5?min whereas for lower working distances (100?µm and 50?µm), the turn-on field increases from 4.74?V/µm to 6.74?V/µm and from 8.79?V/µm to 14.49?V/µm respectively. The turn-on field (E _to) and field enhancement factor (β) were studied as a function working distance (d) and growth time respectively to see the effect of these parameters on field emission properties. The field enhancement factor (β) was also studied as a function of radius of apex curvature (r) . It was found the field enhancement factor (β) decreases with the increase in radius of apex curvature (r) and growth time whereas the value of field enhancement factor (β) increases as working distance (d) increases. On the basis of the dependence of β on radius of apex curvature (r) a relationship of β?∝?r ^?1/2 is fitted.     

Field emission properties of RuO2 thin film coated on carbon nanotubes

Carbon nanotubes (CNTs) have been widely applied in field emission (FE) due to their high geometric aspect ratio and low work function. More recently, researchers have introduced ruthenium dioxide (RuO₂) as a field emitter because of its excellent chemical and thermal stability due to its oxide nature. This study used the surface morphology of CNTs and the field emission (FE) stability of RuO₂ to improve FE characteristics. Since the work functions of CNTs and RuO₂ are very close, this study combined these two elements by applying a thin film of RuO₂ on the CNT surface. In the process of covering the tips of CNTs with a thin film of RuO₂ eventually obtained the best matching of these two elements. The study not only enhanced the FE performance of CNTs but also extended FE lifetime by applying a thin film of RuO₂ on the CNT tips.