Fabrication of Ni-matrix carbon nanotube field emitters using composite electroplating and micromachining

Ni-matrix carbon nanotube (CNT) field emitters have been fabricated by composite electroplating and micromachining (CEMM) at room temperature. Pretreated multi-walled CNT and Ni are deposited onto a Cr/Cu conducting layer by composite electroplating and protruding tips of CNTs are obtained as emitters by etching away a layer of Ni, followed by emitter pixels which are formed by micromachining. Through the process of CEMM, CNTs are vertically embedded in the flat Ni substrate. No further treatment is needed to initiate or augment field emission and the field emitters exhibit good field-emission properties such as high current density (13 mA cm⁻² at an applied electric field of 3.4 V μm⁻¹), low turn-on field (0.53 V μm⁻¹), and good stability (110 h for 10% degradation of current density from 400 μA cm⁻²).     

Horizontally aligned carbon nanotube field emitters having a long term stability

Horizontally aligned carbon nanotube (CNT) field emitters fabricated by electrophoresis deposition and fissure formation techniques show good field emission properties such as high current density, low turn-on voltage and long-term stability. Horizontally aligned multi-walled carbon nanotube (MWCNT) field emitters show an unusual very long-term stability, much better stability than the single-walled carbon nanotube (SWCNT) ones. The cause of the degradation is due to the heat generated by the resistance of CNTs. We were able to prevent effectively the degradation of the horizontally aligned field emitters by using MWCNTs and an additional deposition of aluminum on the CNT films, and the required time for 10% degradation is very long, 121 h.     

In situ oxygen-assisted field emission treatment for improving the uniformity of carbon nanotube pixel arrays and the underlying mechanism

An oxygen-assisted field emission treatment is introduced for improving field emission uniformity of carbon nanotube (CNT) pixel arrays. Oxygen gas is added during the field emission process, and the uniformity of both emission area and brightness of a CNT pixel array are dramatically improved by 83% and 90%, respectively, without reducing emission stability. The underlying physical mechanism for the improvements is attributed to the fact that the oxygen oxidizes the highly emitting CNTs, resulting in their burning out. As a result, the emitting CNTs having a too high current are removed and more and more emitting CNTs with weak current can be stimulated at a higher field, leading finally to a balance of emission from each pixel in the array.     

Highly stable carbon nanotube field emitters on small metal tips against electrical arcing

Carbon nanotube (CNT) field emitters that exhibit extremely high stability against high-voltage arcing have been demonstrated. The CNT emitters were fabricated on a sharp copper tip substrate that produces a high electric field. A metal mixture composed of silver, copper, and indium micro- and nanoparticles was used as a binder to attach CNTs to the substrate. Due to the strong adhesion of the metal mixture, CNTs were not detached from the substrate even after many intense arcing events. Through electrical conditioning of the as-prepared CNT emitters, vertically standing CNTs with almost the same heights were formed on the substrate surface and most of loosely bound impurities were removed from the substrate. Consequently, no arcing was observed during the normal operation of the CNT emitters and the emission current remained constant even after intentionally inducing arcing at current densities up to 70 mA/cm².     

High-current field emission of point-type carbon nanotube emitters on Ni-coated metal wires

The fabrication and field emission characteristics are reported for point-type carbon nanotube (CNT) emitters formed by transferring a CNT film onto a Ni-coated Cu wire with a diameter of 1.24 mm. A Ni layer plays a role in enhancing the adhesion of CNTs to the substrate and improving their field emission characteristics. On firing at 400 °C, CNTs appear to directly bonded to a Ni layer. With a Ni layer introduced, a turn-on electric field of CNT emitters decreases from 1.73 to 0.81 V/μm by firing. The CNT film on the Ni-coated wire produces a high emission current density of 667 mA/cm² at quite a low electric field of 2.87 V/μm. This CNT film shows no degradation of emission current over 40 h for a current density of 60 mA/cm² at electric field of 6.7 V/μm. X-ray imaging of a printed circuit board with fine features is demonstrated by using our point-type CNT emitters.     

High-performance field emission from a carbon nanotube carpet

We have created a field emitter composed of a carbon nanotube (CNT) yarn, which was prepared by direct spinning through chemical vapor deposition and then formed into a carpet structure by tying the yarn to a conductive substrate before cutting it. The structure of the carpet is arranged to induce the tips of the CNT yarn to protrude toward the anode for maximum electron emission. The turn-on field, threshold field, and field enhancement factor of the device are 0.33, 0.48 V/μm, and 19,141, respectively. Extremely low operating electric fields and a high field enhancement factor result from the high density of CNT emitters with high crystallinity, the electrically good contact between the emitters and the substrate, and the effects of the multistage structure. The emission is stable even at a high current density of 2.13 mA/cm², attributed to the strong adhesion between the emitters and the substrate. The emission performance is found to be customizable by adjusting the structure, for example, the CNT pile density. These results are relevant for practical applications, such as large-area flat-panel displays, large-area low-voltage lamps, and X-ray sources.     

Morphology control of three-dimensional carbon nanotube macrostructures fabricated using ice-templating method

3-Dimensional (3D) carbon nanotube (CNT) macrostructures with controlled morphologies were prepared by the ice-templating method. In order to control the assembling of the CNTs into 3D macrostructures, we systematically investigated the parameters critical to the control of the morphology of the 3D CNT macrostructures formed using the ice-templating method. It was found that process parameters such as the initial characteristics of the CNT suspension and its freezing conditions significantly affected the morphologies of the resulting CNT macrostructures. By adjusting the initial characteristics of the suspension of CNTs and its freezing conditions, we could fabricate not only regular 3D CNT macrostructures that consisted of aligned lamellae but also those that had a cellular structure. This is the first instance well-aligned, cellular CNT macrostructures have been prepared using the ice-templating method. Our approach can be used to develop the ice-templating method as a technique for fabricating 3D pore- and structure-controlled CNT macrostructures.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Stable Field Emitters for a Miniature X-ray Tube Using Carbon Nanotube Drop Drying on a Flat Metal Tip

Stable carbon nanotube (CNT) field emitters for a vacuum-sealed miniature X-ray tube have been fabricated. The field emitters with a uniform CNT coating are prepared by a simple drop drying of a CNT mixture solution that is composed of chemically modified multi-walled CNTs, silver nanoparticles, and isopropyl alcohol on flat tungsten tips. A highly thermal- and electrical-conductive silver layer strongly attaches CNTs to the tungsten tips. Consequently, the field emitters exhibit good electron emission stability: continuous electron emission of around 100 μA at 2.3 V/μm has stably lasted over 40 h even at non-high vacuum ambient (~10⁻³ Pa).     

High performance field emission of carbon nanotube film emitters with a triangular shape

We report novel two-dimensional (2D) shaped carbon nanotube (CNT) field emitters using triangular-shaped CNT films and their field emission properties. Using the 2D shaped CNT field emitters, we achieved remarkable field emission performance with a high emission current of 22 mA (equivalent to an emission current density >10⁵ A/cm²) and long-term emission stability at 1 mA for 20 h. We also discuss the field emission behavior of the 2D shaped CNT field emitter in detail.     

Improvement of electron field emission from carbon nanotubes by Ar neutral beam treatment

To improve the field emission properties of screen printed carbon nanotube (CNT) films, an Ar neutral beam was used as one of the surface treatment techniques and the CNT field emission characteristics after the treatment were compared with those after Ar ion beam treatment. The Ar neutral beam treatment enhanced the field emission properties of the CNTs and by decreasing the turn-on field and by increasing emission sites. When the field emission properties were measured after the treatment for 10 s with an energy of 100 eV, the turn-on field decreased from 1.7 to 0.9 V/μm while that after the ion beam treatment increased from 1.7 to 2.8 V/μm showing damage of exposed CNTs due to the intensive bombardment by the positive ions in the beam. The neutral beam treatment appeared to expose more CNT field emitters from the CNT paste without cutting or severely damaging the already exposed long CNT emitters because there were no charged particles in the beam.     

Effect of Purity and Substrate on Field Emission Properties of Multi-walled Carbon Nanotubes

Multi-walled carbon nanotubes (MWNT) have been synthesized by chemical vapour decomposition (CVD) of acetylene over Rare Earth (RE) based AB₂ (DyNi₂) alloy hydride catalyst. The as-grown carbon nanotubes were purified by acid and heat treatments and characterized using powder X-ray diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Thermo Gravimetric Analysis and Raman Spectroscopy. Fully carbon based field emitters have been fabricated by spin coating a solutions of both as-grown and purified MWNT and dichloro ethane (DCE) over carbon paper with and without graphitized layer. The use of graphitized carbon paper as substrate opens several new possibilities for carbon nanotube (CNT) field emitters, as the presence of the graphitic layer provides strong adhesion between the nanotubes and carbon paper and reduces contact resistance. The field emission characteristics have been studied using an indigenously fabricated set up and the results are discussed. CNT field emitter prepared by spin coating of the purified MWNT–DCE solution over graphitized carbon paper shows excellent emission properties with a fairly stable emission current over a period of 4 h. Analysis of the field emission characteristics based on the Fowler–Nordheim (FN) theory reveals current saturation effects at high applied fields for all the samples.     

Co-B纳米合金功能膜化学沉积和电沉积的比较

以硫酸钴、硼氢化钠为主要原料,对电沉积和化学沉积Co-B纳米合金功能膜进行比较,发现尽管电沉积较化学沉积的速度快,但各影响因素和变化规律是一致的。pH值增大和温度的升高会加快沉积速率,络合剂浓度增大则会降低沉积速率,增加硫酸钴、硼氢化钠的浓度都会加快沉积速率,但用化学法沉积时,当硫酸钴、硼氢化钠的浓度超过最大值时,沉积速率反而下降。XRD结果表明,两种方法制备的Co-B纳米合金在镀态下都是非晶态,其结构并不受沉积方法的影响,SEM、STM和AFM观察发现,非晶膜镀层是由纳米相微粒构成微米级的二次颗粒,二次颗粒堆砌形成薄膜。化学沉积得到的颗粒相对电沉积得到的要小一些,两种方法得到的最大颗粒都不超过3 μm。     

Very large cathode current and long term stability of vacuum sealed tubes with engrafted-carbon-nanotube emitters

For the future commercial applications of carbon nanotubes (CNTs) in high power vacuum microwave amplifiers or compact X-ray tubes, we have attempted to fabricate engrafted CNT field emitters on a metallic substrate using both screen printing and chemical vapor deposition. Cobalt nano-grains are doped in the printed CNT paste and act as the catalyst for the engrafted growth of CNTs by the cold wall chemical vapor deposition. Stable cathode current (~ 30 mA) from a small area (~ 1.5 mm²) of engrafted CNT emitters was measured in a vacuum-sealed diode tube. High current density (> 1.6A/cm²) has also gotten in the vacuum sealed tube in which the emitters spread about 0.78 mm² after an aging process that lasts more than 12 h in DC mode with the water cooling of the anode.     

Arc synthesis of double-walled carbon nanotubes in low pressure air and their superior field emission properties

Double-walled carbon nanotubes (DWCNTs) have been effectively synthesized by direct current (DC) arc discharge in low pressure air using a mixture of Fe catalyst and FeS promoter. Compared with conventional arc methods, this method is easier to implement without using expensive high purity gas sources. A tip structural DWCNT film has been successfully fabricated by a mixing process of electrophoresis, electroplating and electrocorrosion. The field emission properties of tip structural nanotube film are significantly increased compared with DWCNT film fabricated by electrophoresis. The turn-on electric field E_to decreases from 1.25 to 0.92 V/μm, the low threshold electric field E_th decreases from 1.45 to 1.13 V/μm, and the field enhancement factor β increases from about 2210 to 4450. Meanwhile, this tip structural CNT film shows remarkably stable within 2% fluctuations for several hours. The high-performance emitter material and preparation technologies are both easy to scale up to large areas.     

Emission characteristics of planar field electron emitters containing carbon nanotubes operating in the high current density mode

Planar field electron emitters containing carbon nanotubes that demonstrate stable emission currents with densities about 1 A/cm² have been fabricated using the chemical vapor deposition method. The analysis of field emission characteristics based on Fowler-Nordheim theory allowed one to calculate not only the field amplification coefficient β, but also the total emission area A of all the emitting nanotubes. Using the value of A and an estimate of the emission area of an individual nanotube fulfilled in this work, the approximate number of emitting nanotubes N before and after the flow of the high density emission current, has been calculated. It has been found that the concentration of the emitting nanotubes N in such field emitters after the high density emission current flow was about 10⁵ cm⁻². Besides this, the location of light radiating nanotubes heated by high density emission currents has been investigated. This has revealed the regions of the emitter surface that gave the main contribution to the electron emission.     

Horizontally aligned carbon nanotube field emitters fabricated on ITO glass substrates

Horizontally aligned carbon nanotube (CNT) field emitters, in which electrons are emitted from the side of CNTs, are fabricated on indium tin oxide (ITO) glass substrates by electrophoretic deposition and fissure formation techniques. A thin film of CNTs is deposited onto an ITO glass plate using an aqueous mixture of CNTs and the cationic detergent cetyltrimethylammonium bromide by applying a negative voltage to the ITO glass plate. Then, an additional layer of sodium dodecyl sulfate (SDS), an anionic detergent, is deposited on the CNT film. This is done using an aqueous solution of SDS by applying a positive voltage. Through the process of firing, CNTs with a clean surface are exposed in the fissures produced. No further treatment is needed to initiate or augment field emission. The CNT field emitters show relatively good field-emission properties such as high current density (11 mA/cm² at an applied electric field of 4.3 V/μm), low turn-on field (2.2 V/μm), and good stability (98 h for 10% degradation of current density from 400 μA/cm²).     

Array geometry, size and spacing effects on field emission characteristics of aligned carbon nanotubes

Microwave plasma-enhanced chemical vapor deposition (MPECVD) has been shown capable of producing vertically aligned mutli-walled CNTs as a result of self-bias of the microwave plasma. These CNTs are relevant to field emission applications. However, it is also known that closely packed or mat-like CNTs are not effective field emitters due to field screening effects among neighboring tubes. In this study, an approach whereby “micro-” patterning of CNT arrays, adjusting their geometry, size and array spacing by conventional photolithography, rather than “nano-” patterning a single CNT by electron-beam lithography, is employed to fabricate efficient emitters with enhanced field emission characteristics. MPECVD with catalysts are used on Si substrate to fabricate micropatterned vertically aligned CNT arrays with various geometries, sizes and spacing. The field emission results show that a circular array with 20 μm spacing has the lowest turn-on field of 2 V/μm at 1 μA/cm² and achieves the highest current density of 100 μA/cm² at 3 V/μm. Investigation on the array spacing effect shows that 10 × 10 μm CNT square array with an array spacing of 20 μm displays the lowest turn-on field of 9 V/μm and achieved a very high current density of 100 mA/cm² at 20 V/μm. Furthermore, the results suggest that the array spacing of the 10 × 10 μm CNT square array can be reduced to at least 20 μm without affecting the field enhancement factor of the emitter. The results clearly indicate further optimization of spacing in the arrays of CNT emitters could result in lower turn-on field and higher current density.     

Synthesis of carbon nanotube/epoxy composite films with a high nanotube loading by a mixed-curing-agent assisted layer-by-layer method and their electrical conductivity

A mixed-curing-agent assisted layer-by-layer method is reported to synthesize carbon nanotube (CNT)/epoxy composite films with a high CNT loading from ∼15 to ∼36 wt.%. The mixed-curing-agent consists of two types of agents, one of which is responsible for the partial initial curing at room temperature to avoid agglomeration of the CNTs, and the other for complete curing of epoxy resin at high temperature to synthesize epoxy composite films with good CNT dispersion. The electrical conductivity of the composites shows a value up to ∼12 S/m, which is much higher than that for CNT/epoxy composites with a low CNT loading prepared using conventional methods.     

高强度碳纳米管改性超滤膜制备

采用液-固相转化法,以聚偏氟乙烯(PVDF)、聚乙烯吡咯烷酮(PVP)和N、N—二甲基乙酰胺(DMAc)为原料,通过改变碳纳米管的含量来制备高强度纳米改性超滤膜。研究发现,碳纳米管不但改善了PVDF超滤膜的膜通量,还增强了其抗拉伸性能,明显提高了其强度;当碳纳米管含量为0.3%时,膜的通量以及强度都达到了最佳性能。