Carbon nanotube field emission cathodes fabricated with chemical displacement plating

A new approach for making field emission cathodes consisting of carbon nanotubes (CNTs) is discussed. The authors used a chemical displacement technique to fabricate field emission cathodes by co-depositing CNTs/nickel composite onto the surface of a zinc-coated soda-lime glass. There are several advantages of this displacement method for preparing field emission cathodes such as the uniform distribution of CNTs in the composite cathodes, low cost of consumed CNTs, low cost of instrument and equipment, feasibility of large-area mass production, and stability of plating solution, which can be used for many times and still remain useful after a long-time storage. The results show that, after the CNT purification and dispersion processes, a CNT content of 1.0 g/L, a pH value of 7.0, and a temperature of 50 ± 3 °C are the optimal process conditions which give better CNT distribution in the CNTs/Ni composite emitter and better field emission performance. The CNTs/Ni composite deposited with a plating solution which has been used for tens of times has an emission effect similar to those deposited with a new solution.     

Water vapor-induced structure modification of vertically-aligned carbon nanotube arrays and successive thin film coating for enhanced field emission properties

Vertically-aligned carbon nanotubes (VCNTs) are used as electron source in various field emission applications owing to its high aspect ratio, chemical inertness, mechanical strength and electrical conductivity. Here, we demonstrate that surface structure modification along with thin film coating enhances the field emission performance, such as turn-on voltage, emission site density, and stability. In the present study, VCNTs with different heights were grown on silicon wafers by thermal chemical vapor deposition followed by the structure modification of VCNTs using capillarity-driven water vapor condensation. We obtained various surface morphologies by varying the water vapor exposure time and heating temperature. In addition, the structure-modified VCNTs surfaces were coated with W and SiO₂ thin films using electron-beam evaporation. It was observed that W-coated VCNTs with modified surface morphology results in the best field emission performance.     

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.     

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.     

碳纳米管阴极的短脉冲爆炸场发射与等离子体膨胀

采用碳纳米管制备了一种强流电子束发射阴极,并对碳纳米管阴极在双脉冲条件下的强流发射性能进行了研究.在双脉冲条件下获得了245 A/cm²的强发射电流密度,阴极的开启时间约为40 ns.采用高速分幅相机和CCD相机对强流电子束在空间和时间的分布进行了研究.研究表明连续脉冲实验时,离子体及其膨胀对发射电子束的强度和分布影响很大,双脉冲时脉冲间隔时间内等离子体的膨胀速率约为8.17 cm/μs.等离子体形成时没有优先位置,电子束发射的局部增强位置是随机的.结果表明碳纳米管阴极可以作为强流阴 关键词： 碳纳米管 爆炸场发射 等离子体膨胀 强流电子束     

Simulation and fabrication of carbon nanotubes field emission pressure sensors

A novel field emission pressure sensor has been achieved utilizing carbon nanotubes (CNTs) as the electron source. The sensor consists of the anode sensing film fabricated by wet etching process and multi-wall carbon nanotubes (MWNTs) cathode in the micro-vacuum chamber. MWNTs on the silicon substrate were grown by thermal CVD. The prototype pressure sensor has a measured sensitivity of about 0.17-0.77 nA/Pa (101-550 KPa). The work shows the potential use of CNTs-based field-emitter in microsensors, such as accelerometers and tactile sensors.     

碳纳米管冷阴极脉冲发射特性及仿真模型研究

针对碳纳米管场致发射冷阴极在微波、毫米波电真空辐射源器件中的应用需求,采用2μs,20 kV的脉冲高压对碳纳米管场致发射冷阴极的脉冲发射特性进行了实验研究.通过改变阴阳极间距,对碳纳米管冷阴极发射电流特性及发生脉冲高压打火后的碳纳米管冷阴极发射特性进行了测试研究.在直径为4 mm的圆形平面碳纳米管冷阴极上获得最大发射电流16 mA,电流密度为127 mA/cm~2.以实验测试数据为基础,结合粒子模拟软件建立碳纳米管冷阴极场致发射仿真模型,给出了该仿真模型的相关参数,为下一步设计研制碳纳米管冷阴极电子光学系统及相关辐射源器件奠定基础.     

Effects on the field emission properties by variation in surface morphology of patterned photosensitive carbon nanotube paste using organic solvent

Photosensitive carbon nanotube (CNT) paste was prepared by 3-roll milling of multi-walled carbon nanotubes (MWNTs), UV-sensitive binder solution, and Ag as filler additives. Arrays of MWNT dots with a diode structure were fabricated by a combination of screen printing method and photolithography using these paste, and acetone utilized as the developer. The MWNT dots were well-defined and the organic binder materials in the dots were partially removed. The MWNT film without a heat treatment showed a high current density of 1.35 mA/cm² at 3.25 V/μm and low turn-on field of 2.2 V/μm at 100 μA/cm². Acetone can be used as an efficient developer to form patterns and to remove the organic residues in patterns, simultaneously.     

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.     

High performance field emission and Nottingham effect observed from carbon nanotube yarn

Vertically aligned CNTs were synthesized on a four inch wafer, followed by the preparation of a CNT yarn. The yarn emitter was found to have an extremely high field enhancement factor, which was confirmed to have originated from multi-stage effect. In addition to superb field emission characteristics, the energy exchange during field emission, called Nottingham effect, was observed from the CNT yarn emitter. A CNT yarn was attached to the thermistor whose resistance depends on temperature. Then, the change of resistance was monitored during the field emission, which enabled us to calculate the energy exchange. It was found that the observed heating originated from both Nottingham and Joule heating. Nottingham heating was dominant at low current region while Joule heating became larger contribution at high current region. Very large Nottingham region of up to 33.35 mA was obtained, which is due presumably to the high performance field emission characteristics of a CNT yarn. This is believed to be an important observation for developing reliable field emission devices with suppressed Joule heating effect.     

大电流密度碳纳米管场致发射阴极阵列的研制

 设计了一种由TiN，Al，Fe和牺牲层构成的堆栈式催化剂层结构，采用微波等离子体化学气相沉积法实现碳纳米管阵列高速笔直生长。SEM和TEM结果表明，生长出来的碳纳米管为典型的多壁碳纳米管，长度和直径均匀，排列整齐并垂直于基底，生长速率大于5 μm/min，晶格缺陷少。场致发射测试结果表明：碳纳米管的发射阵列具有良好的电流发射稳定性，最大电流密度大于6 A/cm2。紫外光电子能谱法（UPS）测试出碳纳米管的功函数为4.59 eV，则相应的场致发射陈列的场增强因子大于1 400。     

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.     

Flame synthesis of carbon nanotubes for panel field emission lamp

Multi-walled carbon nanotubes (CNTs) were synthesized on the surfaces of Ni-alloy plated Fe-wires with the diameter of 2 mm using a conventional laboratory ethanol (C₂H₅OH) flame method at 560 °C. SEM showed that the product had bush-shaped micron-structures with diameters from 100 to 450 nm and lengths of over 1.0 μm. TEM revealed that the micron-structures were composed of multi-walled nanotube bundles with the diameters of about 50 nm. The test on the diode configuration field emission of the Fe-wire arrays was performed. The onset electric field was 2.95 V/μm and the emission current can reach 50 mA/cm² at an electric field of 9 V/μm. The average fluctuation of the emission current density was less than 7%. The result suggests that the field emission was uniform and the present technique was feasible to fabricate Panel Field Emission Lamp (PFEL) with arrays of carbon nanotubes. PFEL has the advantages of high luminescence as well as stability, and thus, it can be used to replace ordinary lights.     

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.     

Synthesis of amorphous carbon nanowalls by DC-PECVD on different substrates and study of its field emission properties

Amorphous carbon thin films with quasi vertical nanowall-like morphologies have been synthesized via direct current plasma enhanced chemical vapor deposition on both copper and silicon substrates with acetylene as a carbon precursor. The deposition temperature and pressure were maintained at 750 °C and 5 mbar respectively. The morphology of the as-prepared samples has been investigated with the help of a field emission scanning electron microscope and an atomic force microscope, both revealing nanowall-like morphologies with thicknesses of the walls ∼6-15 nm. The as-prepared carbon nanowalls showed good field electron emission with a turn-on field as low as 1.39 V/μm. The effect of inter-electrode distance on the field electron emission has also been studied in detail.     

Improve the field emission uniformity of carbon nanotubes treated by ball-milling process

Carbon nanotubes (CNTs) deposited by chemical vapor deposition (CVD) were treated by ball milling. The morphologies and field emission properties of the treated CNTs depending on milling time were studied. The emission turn-on field is increased, and the field emission current density is reduced, when the milling time increased from 0.5 to 3 h. The as-deposited long CNTs were cut to short CNTs (∼1 h) and micro-particles (>1 h) with increasing of the milling time. It is found that the optimized milling time is 0.5-1 h, the treated CNTs showed excellent field emission properties, such as low turn-on field, high emission current density and uniform luminescence spots distribution.     

A comparative study of thermionic emission from vertically grown carbon nanotubes and tungsten cathodes

Thermionic emission from vertically grown carbon nanotubes (CNTs) by water-assisted chemical vapor deposition (WA-CVD) is investigated. I-V characteristics of WA-CNT samples exhibit strong Schottky effect leading to field proportionality factor β ∼ 10⁴ cm⁻¹in contrast to β ∼ 200 cm⁻¹ for the bare tungsten substrate. Non-contact atomic force microscopy imaging of CNT samples show propensity of nanoasperities over a scale of micron size over which the tungsten surface is seen to be atomically smooth. The values of root mean-square roughness for CNTs and W were found to be 24.2 nm and 0.44 nm respectively. The Richardson-Dushman plots yield work function values of Φ_CNT ? 4.5 and Φ_W ? 4.3 eV. Current versus time data shows that CNT cathodes are fifteen times noisier than tungsten cathode presumably due to increased importance of individual atomic events on the sharp CNT tips of bristle like structures. Power spectral density of current exhibited 1/f^ξ behavior with ξ ? 1.5, and 2 for W and CNTs. The former suggests surface diffusion whereas the latter indicates adsorption/desorption of atomic/molecular species as a dominant mechanism of noise generation.     

Effects of total CH4/Ar gas pressure on the structures and field electron emission properties of carbon nanomaterials grown by plasma-enhanced chemical vapor deposition

The effects of total CH₄/Ar gas pressure on the growth of carbon nanomaterials on Si (1 0 0) substrate covered with CoO nanoparticles, using plasma-enhanced chemical vapor deposition (PECVD), were investigated. The structures of obtained products were correlated with the total gas pressure and changed from pure carbon nanotubes (CNTs) through hybrid CNTs/graphene sheets (GSs), to pure GSs as the total gas pressure changed from 20 to 4 Torr. The total gas pressure influenced the density of hydrogen radicals and Ar ions in chamber, which in turn determined the degree of how CoO nanoparticles were deoxidized and ion bombardment energy that governed the final carbon nanomaterials. Moreover, the obtained hybrid CNTs/GSs exhibited a lower turn-on field (1.4 V/μm) emission, compared to either 2.7 V/μm for pure CNTs or 2.2 V/μm for pure GSs, at current density of 10 μA/cm².     

An improved planar-gate triode with CNTs field emitters by electrophoretic deposition

An improved planar-gate triode with carbon nanotubes (CNTs) field emitters has been successfully fabricated by conventional photolithography, screen printing and electrophoretic deposition (EPD). In this structure, cathode electrodes and ITO arrays linked with gate electrodes were interdigitated and paralleled on the same plane although the gate electrodes and cathode electrodes were isolated by dielectric layer, a so-called improved planar-gate triode structure. An electrophoretic process was developed to selectively deposit CNTs field emitters onto cathode electrodes in the CNTs suspension by an applied voltage between the gate electrodes and cathode electrodes. The optical microscopy and FESEM image showed that the CNTs emitters with the uniform packing density were selectively defined onto the cathode electrodes. In addition, field emission characteristics of an improved planar-gate triode with CNTs field emitters were investigated. The experiment results indicated that the turn-on voltage of this triode structure at current density of 1 μA/cm² was approximately 55 V. The anode current and gate current came to 396 μA and 325 μA, at gate voltage and anode voltage of 100 V and 4000 V, respectively and at the anode-cathode spacing of 2000 μm. The emission image became brighter and the luminous image with dot matrix on the anode plate obviously increased with the increase of the gate voltage. Moreover, the emission current fluctuation was smaller than 5% for 11 h, which indicated that the improved planar-gate triode has a good field emission performance and long lifetime.     

Field emission characteristics of screen-printed carbon nanotubes cold cathode by hydrogen plasma treatment

Selective plasma etching and hydrogen plasma treatment were introduced in turn to improve field emission characteristics of screen-printed carbon nanotubes (CNTs) cold cathode, which was prepared by using slurry of mixture of multi-wall CNTs, organic vehicles and inorganic binder, i.e. silicon dioxide sol. The results show that selective plasma etching process could effectively remove parts of surface inorganic vehicle (SiO₂) layer and expose more smooth and clean CNTs on cathode surface, which could significantly decrease the operating field of CNTs cathode. There are some nanoparticles emerging on the out of CNTs wall after hydrogen plasma treatment, which are equivalent to increase field emission point of cathode. At the same time, these nanoparticles can increase the local electric field of CNTs, which can decrease operating voltage of CNTs cathode and improve uniformity field emission.