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.     

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。     

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.     

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.     

The growth of multi-walled carbon nanotubes on natural clay minerals (kaolinite, nontronite and sepiolite)

The suitability of clay minerals - kaolinite, nontronite and sepiolite - is studied for synthesis of nanocomposites based on carbon nanotubes. Particles of iron were used as catalysts. Prior to synthesis, kaolinite and sepiolite were doped by the catalytically active metal, whereas in the case of nontronite the presence was used of this metal in the matrix of this mineral. Synthesis of CNTs was performed by hot filament chemical vapor deposition method. The produced nanocomposites were examined by transmission and scanning electron microscopies and energy dispersive X-ray spectroscopy. The experiment verified the potential of the three microcrystalline phyllosilicates for the growth of carbon nanotubes. Under the same technology conditions, the type of catalyst carrier affects the morphology and structure of the nanotube product markedly.     

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.     

Electron emission studies of CNTs grown on Ti and Ni containing amorphous carbon nanocomposite films

Carbon nanotubes (CNTs) were grown successfully on the as-deposited dual metal (Ti and Ni) embedded films using a radio frequency plasma-enhanced chemical vapor deposition system. The microstructure of CNTs grown on the dual metal films proved to be heavily dependent on the percentages of metals included, varying both in size and in density. Electron emission tests carried out on the films with CNTs grown showed that the threshold field was dependent on the surface morphology of the CNTs, with the lowest threshold field at 3.5 V/μm from 2.5% Ti/Ni film with CNTs. The field enhancement factor, β, of the emitting tips was also calculated from the Fowler–Nordheim plots, where CNTs from the 2.5% Ti/Ni film gave the highest field enhancement factor. However, it was observed that films with a single metal of either Ti or Ni did not manage to grow CNTs, possibly due to a lack of catalyst centres at the surface of the films. It was believed that the Ni nanoclusters acted as catalysts centres giving a rather uniform but randomly orientated type of CNTs. Results obtained pointed that the fabricated nanocomposite material could be a possible choice for cold cathode emitters and the Ti/Ni mixture could be an effective composite for controlling the CNT density.     

Aligned carbon nanotubes catalytically grown on iron-based nanoparticles obtained by laser-induced CVD

Iron-based nanoparticles are prepared by a laser-induced chemical vapor deposition (CVD) process. They are characterized as body-centered Fe and Fe₂O₃ (maghemite/magnetite) particles with sizes ≤5 and 10 nm, respectively. The Fe particles are embedded in a protective carbon matrix. Both kind of particles are dispersed by spin-coating on SiO₂/Si(1 0 0) flat substrates. They are used as catalyst to grow carbon nanotubes by a plasma- and filaments-assisted catalytic CVD process (PE-HF-CCVD). Vertically oriented and thin carbon nanotubes (CNTs) were grown with few differences between the two samples, except the diameter in relation to the initial size of the iron particles, and the density. The electron field emission of these samples exhibit quite interesting behavior with a low turn-on voltage at around 1 V/μm.     

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.     

A simple method for creating nanotube field emitters from a surfactant dispersion

A new method has been developed for depositing aligned ropes of single-walled nanotubes (SWNTs) such that a significant number of ropes protrude normally from the surface. The resulting surface has excellent field emission characteristics owing to the high local fields generated at the tips of the protruding nanotubes. Further development of the technique may lead to the construction of a reasonably homogeneous surface bristling with nanotube ropes, which could allow spatially resolved neutral atom detection via field ionization.     

Gas phase kinetic and optical emission spectroscopy studies in plasma-enhanced hot filament catalytic CVD production of carbon nanotubes

Optical emission spectroscopy (OES) is used as the main experimental tool for comparison with simulations of the plasma and gas phase composition during plasma-enhanced hot filament catalytic chemical vapor deposition (PE HF CCVD) growth of carbon nanotubes (CNTs). Calculated concentration of more than 45 species in model of the CVD reactor is acquired by Chemkin™ software. Study of different conditions is performed and a close relationship can be found between the nature and the growth rate of carbon nanostructures and the concentration of the active gas phase species. Moreover it is shown that significant changes in the density and morphology of the CNTs grown in the presence of NH₃ could be mainly explained by the gas phase formation of CN and HCN.     

Stable electron field emission from carbon nanotubes emitter transferred on graphene films

Carbon nanotubes (CNTs) arrays grown by microwave plasma enhanced chemical vapor deposition (MPCVD) method was transferred onto the substrate covered with graphene layer obtained by thermal chemical vapor deposition (CVD) technology. The graphene buffer layer provides good electrical and thermal contact to the CNTs. The field emission characteristics of this hybrid structure were investigated in this study. Compared with the CNTs arrays directly grown on the silicon substrate, the hybrid emitter shows better field emission performance, such as high emission current and long-term emission stability. The presence of this graphene layer was shown to improve the field emission behavior of CNTs. This work provides an effective way to realize stable field emission from CNTs emitter and similar hybrid structures.     

Enhanced field emission characteristics of boron doped diamond films grown by microwave plasma assisted chemical vapor deposition

Boron doped diamond films were synthesized on silicon substrates by microwave plasma chemical vapor deposition (MPCVD) technique. The effect of B₂O₃ concentration varied from 1000 to 5000 ppm on the field emission characteristics was examined. The surface morphology and quality of films were characterized by scanning electron microscope (SEM) and Raman spectroscopy. The surface morphology obtained by SEM showed variation from facetted microcrystal covered with nanometric grains to cauliflower of nanocrystalline diamond (NCD) particles with increasing B₂O₃ concentration. The Raman spectra confirm the formation of NCD films. The field emission properties of NCD films were observed to improve upon increasing boron concentration. The values of the onset field and threshold field are observed to be as low as 0.36 and 0.08 V/μm, respectively. The field emission current stability investigated at the preset value of ∼1 μA is observed to be good, in each case. The enhanced field emission properties are attributed to the better electrical conductivity coupled with the nanometric features of the diamond films.     

Fabrication of a three-dimensional complex carbon nanoneedle from carbon nanowalls

A three-dimensional complex carbon nanoneedle has been fabricated from carbon nanowalls by a direct current plasma chemical vapor deposition system. Sample grown on stainless wire substrate pretreated with the mixing powders of diamond and molybdenum exhibits novel three-dimensional complex nanostructure, the center of which is a carbon nanoneedle, and many carbon nanowalls growing from the needle. The density of unique nanostructure emitters was about 5 × 10⁷/cm². The I-V characteristic addressed an emission current density of 314 mA/cm² at the electric field of 2.5 V/μm.     

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.     

掺杂对碳纳米管拉曼光谱及场发射性能的影响

采用高温热解法在860℃分别制备出了镓、氮以及硼和氮掺杂的碳纳米管,提纯后利用丝网印刷工艺分别将它们制备成薄膜,并测试了它们的拉曼光谱与场发射性能。测试结果表明,掺杂纳米管的缺陷密集度比纯碳纳米管明显增大,而它们的场致电子发射性能则与掺杂元素的性质密切相关。镓和氮掺杂的纳米管均具有非常优异的场发射性能,而硼和氮共掺杂的纳米管的场发射性能很差。掺杂引起碳纳米管费米能级附近能态密度的变化及功函数的降低是其具有优异场致电子发射性能的主要原因。     

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.     

Influence of high-energy electron irradiation on field emission properties of multi-walled carbon nanotubes (MWCNTs) films

The effect of very high energy electron beam irradiation on the field emission characteristics of multi-walled carbon nanotubes (MWCNTs) has been investigated. The MWCNTs films deposited on silicon (Si) substrates were irradiated with 6 MeV electron beam at different fluence of 1×10¹⁵, 2×10¹⁵ and 3×10¹⁵ electrons/cm². The irradiated films were characterized using scanning electron microscope (SEM) and micro-Raman spectrometer. The SEM analysis clearly revealed a change in surface morphology of the films upon irradiation. The Raman spectra of the irradiated films show structural damage caused by the interaction of high-energy electrons. The field emission studies were carried out in a planar diode configuration at the base pressure of ∼1×10⁻⁸ mbar. The values of the threshold field, required to draw an emission current density of ∼1 μA/cm², are found to be ∼0.52, 1.9, 1.3 and 0.8 V/μm for untreated, irradiated with fluence of 1×10¹⁵, 2×10¹⁵ and 3×10¹⁵ electrons/cm². The irradiated films exhibit better emission current stability as compared to the untreated film. The improved field emission properties of the irradiated films have been attributed to the structural damage as revealed from the Raman studies.     

多壁碳纳米管阵列场发射研究

研究了Ar离子束轰击及温度对多壁碳纳米管阵列场发射性能的影响.经Ar离子轰击35min后，发现阵列顶端的Fe催化剂颗粒明显减少，弯曲的顶部被轰击掉，使碳纳米管的场发射电流明显减小而场发射像无明显改变.温度的增加引起碳纳米管的场发射电流也随之增加.还研 究了在透明阳极技术中涂在阳极的荧光粉对场发射电流的影响.对同一碳纳米管阵列样品，发现涂有荧光粉的透明阳极使测量到的场发射电流大幅度减小，只是未涂荧光粉阳极电流的 1/30左右.直接用二氧化锡导电膜作阳极时，测得样品的开启场强为1.0V/μm.沉积了荧光粉的二 关键词： 多壁碳纳米管 场发射     

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.