硅纳米孔柱阵列的场致电子发射

测试了用水热技术制备的硅纳米孔柱阵列(silicon nanoporous pillar array(简称Si-NPA))的场致发射性能.测试结果显示,Si-NPA的开启电场为约1.48V/μm;在5V/μm的外加电场下,其发射电流密度为28.6μA/cm~2;在外加电场4.4V/μm时,其电流浮动率为13%.Si-NPA发射性能增强的原因是由于其独特的表面形貌和结构所致.     

Accelerated resistive humidity sensing properties of silicon nanoporous pillar array

Silicon nanoporous pillar array (Si-NPA), with micro/nanometer composite structure, was prepared by hydrothermally etching single crystal silicon. Resistive humidity sensors were fabricated through evaporating coplanar interdigital aluminium electrodes on Si-NPA and the humidity sensing properties were tested. It was shown that with relative humidity changing from 11.3% to 94.6%, a resistance device response over one order of magnitude with response time less than 1 s was achieved at frequency of 1 kHz. This extraordinary property was mainly attributed to the unique morphology of Si-NPA, i.e., the regular pillar array provided an effective pathway for vapor transportation and the nanoporous structure of the pillars greatly enlarged the sensing areas.     

Room-temperature H2S gas sensing properties of carbonized silicon nanoporous pillar array

Through thermally treating silicon nanoporous pillar array (Si-NPA) in a graphite crucible in a vacuum furnace at 1100 °C, a continuous thin film composed of cubic SiC nanoparticles was prepared and its room-temperature resistive sensing properties were measured. The sensor was found to be with high sensitivity and an upper limit concentration of 1200 ppm for H₂S detection. Through carrying out the experiments of adsorption-desorption dynamic cycles and long-time air-ambient storage, the sensor was demonstrated to be with high repeatability and long-term stability. The response and recovery times were determined to be ~ 123 and ~ 114 s, respectively. The sensing mechanism was put forward through analyzing the possible adsorption modes of H₂S molecules on SiC/Si-NPA. The existence of the detecting limit concentration was attributed to the single-layer adsorption of H₂S molecules, whose quantity was restricted by the effective adsorption sites formed on SiC/Si-NPA. Our results show that SiC/Si-NPA might be an ideal sensing material for fabricating low-concentration H₂S gas sensors.     

铬酸溶液后处理增强碳纳米管的场发射特性

采用铬酸溶液对碳纳米管进行后处理,旨在修饰碳纳米管的表面形态及改变碳纳米管的表面结构,进一步增强碳纳米管的场发射特性.铬酸溶液后处理与传统以硝酸后处理的厅法不同之处在于,铬酸溶液可以更有效率地与非品质碳及碳纳米管发生化学反应.可以预期碳纳米管经过铬酸溶液处理后,碳纳米管的表而形态、化学组成及场发射特性会产生很大的变化.场发射的数据显示,经铬酸溶液处理20 min的碳纳米管场发射电流比未经过铬酸溶液处理的场发射电流有明显的增加.然而,长时间的铬酸溶液处理也会降低碳纳米管场发射特性.经铬酸溶液处理20min的碳纳米管场发射电流增强原因主要为适度的铬酸溶液处理可以改变碳纳米管的表面形态,使碳管的表面密度增大、场发射功函数降低.但过长时间的铬酸溶液后处理,又会造成碳纳米管数目减少及表面结构受到损害,导致碳纳米管场发射特性变差.     

Enhancement of field emission property from hills-like carbon nanotubes film

Improved field emission property of carbon nanotubes (CNTs) is achieved by using NiTi alloy film as catalyst under optimized condition. The NiTi alloy films are prepared by magnetron co-sputtering process and the CNTs films are synthesized by thermal chemical vapor deposition. With the increase of the Ni/Ti ratio from 19 at.% to 95 at.%, the CNTs density increases from discrete cluster to dense network, and the optimized field emission property of CNTs film is found at the medium density. However, the field emission property is significantly enhanced when the Ni/Ti ratio is about 76 at.%, and it is supposed to attribute to the combined effect of the hills-like surface enhancement and the intrinsic emission properties of CNTs.     

Field emission from carbon nanotubes in DC and pulsed mode

Multi-wall Carbon Nanotube (CNT) emitters were tested in a combined diode-RF electron gun. Field emission of the nanotubes was observed at 5-30 MV/m, using a 250 ns FWHM long pulse with a peak voltage of 80-470 kV. The field emission threshold is compatible with that found from previous DC testing. We have extracted from a continuous field emitter up to a nanoCoulomb of charge and measured an emittance of 4 mm mrad with a 2 pC electron beam. The total charge emission during RF operation, using the 1.5 GHz, 2 cell RF structure, was found dependent on its period. RF operation showed that back bombarding electrons with up to 5 MeV did not impair the emission stability of the CNTs.     

真空度对纳米碳管场发射性能的影响

研究了单壁纳米碳管(SWNTs)、双壁纳米碳管(DWNTs)和多壁纳米碳管(MWNTs)在不同真空度下的场发射性能。在超高真空条件下(2.0×10-7Pa),以上三种材料均表现出良好的稳定性;而在高真空条件下(1.0×10-4Pa),三种材料的场发射稳定性有不同程度的下降。通过控制系统真空度在2.0×10-7Pa～1.3×10-3Pa范围内逐渐变化,考察了真空度对纳米碳管场发射性能的影响及其机制,提出适合于SWNTs、DWNTs和MWNTs场发射性能测试和应用的真空度下限分别为6.0×10-5Pa、1.0×10-4Pa和5.7×10-4Pa。     

Effect of patterned and aligned carbon nanotubes on field emission properties

The field emission (FE) properties of carbon nanotubes (CNTs) films with different morphologies were simulated and examined. Based on the FE mechanism of aligned CNTs’ emitter the theoretical analysis exhibited the following relations: the FE enhancement factor with the distance between the emitters, the electric field with work function, and the work function with FE enhancement factor. Using the structure-induced CNTs growing method and theoretical results the direction of aligned CNTs could be controlled and the special morphology with different aligned CNTs’ film could be fabricated. Comparing to the experimental results (the medium density and patterned CNTs’ emitters) with the theoretically calculating results the I-V curves had the same trend with only 0.05 mA deviation. Based on the better experimental methods and means the accurate of formula could be further improved by modified the FE properties (Φ, β).     

金/硅纳米孔柱阵列的场发射

利用浸溃技术在硅纳米孔柱阵列(silicon nanoporous pillar array(简称Si-NPA))上制备了复合纳米薄膜Au/Si-NPA.测试了其场发射性能.测试结果显示,Au/Si-NPA的开启电场为约2V/μm;在7.59V/μm的外加电场下,其发射电流密度为67μA/cm2;在外加电压2000V时,其电流浮动率为21%.导致Au/Si-NPA优良的发射性能是由于其独特的表面形貌和结构所致.     

High-Current-Density field emission from self-heating printed carbon nanotubes

High-current-density field emitters are considered as the potential and necessary components for compact high definition x-ray sources and high-power cold cathode microwave amplifiers. In this report, high-current-density field emission from self-heating printed carbon nanotubes is introduced. Large emission current causes large heat that increases the temperature of the emitters. The temperature is estimated to be more than ~1600 K. Localized surface field and high temperature both drive more electrons escaping from the emitters, and the maximum current density is larger than ~2.7 A/cm² that will satisfy the need of most vacuum electron devices including x-ray sources and microwave electron devices.     

基于单块WO3纳米孔柱阵列的微型湿度感应器

采用水热法,在160℃下反应48h制得方块状的WO3纳米孔柱阵列,并使用扫描电镜和X射线衍射仪对样品进行了物相和形貌分析。为验证该材料在湿度感应方面的结构优势,制作了基于单块WO3方块的微型湿度感应器。测试结果显示,在相对湿度为20%～75%的范围内,感应器的电阻几乎随相对湿度的增加而线性减小;感应器对在20%和60%两者间周期性变化的湿度表现出极快速的响应（约2s）,且具有良好的稳定性和重复性。分析表明质子导电对该感应器的湿度感应起主要贡献。     

Preparation technique for copper-plating on Si nanoporous pillar array

Silicon nanoporous pillar array (Si-NPA) is prepared by hydrothermally etching method. The copper/silicon nanocomposite thin film (Cu/Si-NPA) is obtained utilizing a reductive deposition method where Si-NPA acts both as a reducing agent and as a substrate. Microstructural analysis indicates that Si-NPA is composed of large quantities of well-separated, quasi-identical silicon pillars which are uniform and perpendicular to the surface. The pillar surface is nanoporous and the pore wall is composed of silicon nanocrystallites with a size about 4 nm. Cu/Si-NPA inherits the morphological characteristic of Si-NPA. The density of the Cu nanoparticles changes alternatively with the geometrical sites of Si-NPA, which leads to the formation of crater-like structures. These results indicate that Si-NPA might be used as an ideal template for synthesizing metal/silicon nanocomposite systems.     

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.     

尖锐端头碳纳米管的制备与场发射特性

采用氢电弧法制备了尖锐端头的碳纳米管,获得了具有三种特殊形貌的尖端,即锥形、颈缩形和铅笔状尖端.该特殊彤貌的彤成可归因于在原料中加入硅粉进而形成的结构缺陷.研究了所得碳纳米管的场发射特性,发现其阈值电场较低,仅为3.75V/mm;场发射电流密度可高达～1.6×105A/cm2;且场发射稳定性好.以上优异的场发射性能归结于该碳纳米管具有良好的结构完整性和独特的尖端结构特征.

Abstract：

Carbon nanotubes (CNTs)with sharp tips were synthesized by a hydrogen arc discharge method. Three unusual morphologies,i.e. ,a cone-shaped tip,a suddenly-shrinking tip,and a pencil point-like tip were observed. These novel tip structures are considered to be related to the addition of a small amount of silicon powder in the raw material,which may introduce structural defects in the CNTs. The field emission properly of the sharp-tip CNTs was investigated,and a low threshold electric field of 3.75 V/m,a high field emission current density of ～1.6× 105 A/cm2,and a good emission stability were demonstrated. The superior field emission performance of the CNTs can be attributed to their good crystallinity and unique tip structures.     

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 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.     

Study of the ability to field emission from diamond-like carbon layers and carbon nanotubes

The aim of this work was to study the relationship between parameters of the electron field emission and the film deposition method. In this study two methods were applied: classical radio frequency plasma-assisted chemical vapor deposition (RF PACVD) to produce diamond-like carbon (DLC) layers and chemical vapor deposition (CVD) to produce carbon nanotubes (CNT). DLC layers were grown on n-type silicon substrates and CNT were grown on n-type and p-type silicon substrates.Atomic force microscopy (AFM) and Raman spectroscopy were used to investigate the physical and chemical parameters of DLC films after deposition process. The electrical parameters of capacitors with the DLC layer as an insulator were extracted from the capacitance-voltage (C-V) and current-voltage (I-V) characteristics. Measurements of the field emission were performed after characterization of the layer properties.     

热化学气相沉积法在硅纳米丝上合成碳纳米管

利用热化学气相沉积法在负载不同厚度催化剂的硅纳米丝(SiNW)表面生长碳纳米管(CNTs),探讨了生长条件对所合成SiNW-CNT的结构和场发射特性的影响.这种类似树状的三维结构具有较高碳纳米管表面密度及降低的电场筛除效应等潜在优势.使用拉曼光谱( Raman)、电子显微镜(SEM)、透射电子显微镜(TEM)、能量扩散分光仪(EDS)分析了碳纳米管的结构性质,并在高真空下施加电场测得碳纳米管的场发射特性.结果表明:随硅纳米丝上负载催化剂镍膜厚度的变化,所合成碳纳米管的表面特性、结晶结构及功函数改变,导致电子发射难易程度的改变,进一步影响碳纳米管的场发射特性.     

The influence of organophilic clay on field electron emission uniformity and lifetime of screen printed carbon nanotube film

The effect of adding clay, modified by a silane coupling agent, into the carbon nanotube (CNT) paste on the field electron emission and a lifetime of screen printed CNT film was studied. The composition of organophilic clay and CNTs was characterized by a combination of X-ray diffraction, and scanning electron microscopy. The incorporation of clay improved the dispersivity, adhesiveness, and conductive networking of paste, therewith enhancing the field emission's uniformity and stability. The improvement of this gas barrier on the CNT film by clay loading prevents emission degradation.     

Room temperature mass production of carbon nanotube field emission micro-cathode arrays using electroplating of a CNT/Ni composite followed by micro-machining

A room temperature fabrication method for the mass production of carbon nanotube (CNT) field emission micro-cathode arrays is reported. The technique combines electroplating of a CNT/Ni composite and micro-machining. This method combines the advantages of direct growth and screen printing conventionally used to fabricate such structures and avoids their disadvantages. Due to its integration and room temperature processing, the technique is proven to be advantageous in mass production and low cost. Results of field emission testing show that the CNT micro-cathodes have excellent field-emission properties, such as high current density (15.7 mA/cm²), field enhancement factor (2.4 × 10⁶/cm), and good stability (109 h for 10% degradation of current density from 400 μA/cm²).