Synthesis, field emission and glucose-sensing characteristics of nanostructural ZnO on free-standing carbon nanotubes films

Free-standing multiwall carbon nanotubes (MWNTs) films were coated, using chemical vapor deposition method, with a thin layer of nanostructural ZnO. The morphology and crystal structure of the as-grown products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering analyses. Field emission (FE) results demonstrated that the needle-like and spherical ZnO-MWNTs composite structure films possessed good performance with a turn-on field of 1.3, 2.2 V μm⁻¹ and a threshold field of 2.6, 4.5 V μm⁻¹, respectively. The glucose-sensing characteristic has also been studied. The multi-layer electrode (PDDA/GOx/ZnO/MWNTs) exhibited significant electrocatalysis to the oxidation and reduction of H₂O₂ than the PDDA/GOx/MWNTs electrode, which provided wide potential applications in clinical, environmental, and food analysis.     

Synthesis and field emission of patterned ZnO nanorods

A simple and self-catalytic method has been developed for synthesizing finely patterned ZnO nanorods on ITO-glass substrates under a low temperature of 500 °C. The patterned ZnO nanorod arrays, a unit area is of 400 × 100 μm², are synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized ZnO nanorods are characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism of formation of ZnO nanorods is also discussed. The measurement of field emission (FE) reveals that the as-synthesized ZnO nanorods arrays have a turn-on field of 3.3 V/μm at the current density of 0.1 μA/cm² and a low threshold field of 6.2 V/μm at the current density of 1 mA/cm². So this approach must have a potential application of fabricating micropatterned oxide thin films used in FE-based flat panel displays.     

Synthesis and efficient field emission of ZnO nanoinjectors

ZnO nanoinjectors were synthesized on Au-coated Si substrate by direct thermal evaporation of zinc powder at a low temperature of 600 °C and atmospheric pressure. Field-emission scanning electron microscopy and X-ray diffraction were applied to study the structural characteristics of the sample. The result indicated that the nanoinjector sample consisted of single-crystalline wurtzite structures which were preferentially oriented in the 0 0 1 direction. The field emission of the sample started at a turn-on field of 1.5 V/μm at a current density of 1 μA/cm², while the emission current density reached about 1 mA/cm² at an applied field of 5.0 V/μm.     

Synthesis and field emission of novel ZnO nanorod chains

A new aqueous chemical growth method for generation of ZnO nanorod chains, transformed from ZnO micro dumbbell, has been developed. The novel structure and morphology of the as-synthesized ZnO micro dumbbell and ZnO nanorod chains are characterized using X-ray diffraction and scanning electron microscopies. Field emission characterization shows that the turn-on fields for the ZnO nanorod chains and micro dumbbell are 2.7 and 5.0 V/μm, respectively. The field enhancement factor β was estimated to be about 2194 for ZnO nanorod chains. The findings imply that ZnO nanorod chains may be suitable for cold-cathode electron source applications.     

CNx纳米管的制备、结构观察及低场致电子发射性能研究

采用高温热解法，以乙二胺为前驱液，在沉积有铁催化剂的p型硅（111）基底上制备出了定向生长的CNx纳米管.利用扫描电子显微镜、高分辨率透射电子显微镜和拉曼光谱对CNx纳米管进行了形貌观察和表征.CNx纳米管的高度在20?μm左右，直径在50—100nm之间，具有明显的“竹节状”结构，结晶有序度较差.对CNx纳米管薄膜进行低场致发射性能测试：外加电场为1.4V/μm，观察到20?μA /cm2发射电流，外电场升至2.54V/μm时发射电流达到1.280mA/cm2，在较高外电场下，没有发现电流“饱和”.这比 关键词： CNx纳米管 高温热解 “竹节状”结构 场致发射     

CNx纳米管的制备、结构观察及低场致电子发射性能研究

采用高温热解法 ,以乙二胺为前驱液 ,在沉积有铁催化剂的p型硅 (1 1 1 )基底上制备出了定向生长的CNx 纳米管 .利用扫描电子显微镜、高分辨率透射电子显微镜和拉曼光谱对CNx 纳米管进行了形貌观察和表征 .CNx 纳米管的高度在 2 0 μm左右 ,直径在 5 0— 1 0 0nm之间 ,具有明显的“竹节状”结构 ,结晶有序度较差 .对CNx 纳米管薄膜进行低场致发射性能测试 :外加电场为 1 4V μm ,观察到 2 0 μA cm2 发射电流 ,外电场升至 2 5 4V μm时发射电流达到1 2 80mA cm2 ,在较高外电场下 ,没有发现电流“饱和” .这比相同实验条件下改变前驱液制备出的碳纳米管和硼碳氮纳米管的场发射性能优越 .还在“竹节状”结构的基础上对CNx 纳米管的场致电子发射机理进行了讨论     

Synthesis of ZnO films with a special texture and enhanced field emission properties

ZnO films with special textures are fabricated on Mo-coated Al₂O₃ ceramic substrates by the catalyst-free electron beam evaporation method, and the as-deposited films are treated by hydrogen plasma. It is found that the surface morphologies of the films are changed significantly after hydrogen plasma treatment and that the films consist of vertically standing and intersecting nanosheets. A lower turn-on field of 1.2 V/μm and an enhanced current density ～0.11 mA/cm² at 2.47 V/μm are achieved. The low threshold field and the high emission current density are attributed primarily to the unique shape and smaller resistivity of the ZnO nanosheet films.     

Synthesis, characterization and low field emission of CNx nanotubes

Aligned CN_x nanotubes were fabricated by pyrolyzing ethylenediamine on p-type Si(1 1 1) substrates using iron as the catalyst. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrum (XPS) and Raman spectroscopy were used to characterize the CN_x nanotubes. The CN_x nanotubes with the average length of 20 μm and diameters in the range of 50–100 nm have the “bamboo-like” structure and worse crystalline order. The low-field emission measurements of the CN_x nanotubes indicated that 20 μA/cm² current densities were observed at an electric field of 1.4 V/μm and 1.280 mA/cm² were obtained at 2.54 V/μm. The CN_x nanotubes exhibit better field emission properties than the carbon nanotubes and the BCN nanotubes. The emission mechanism of CN_x nanotubes is also discussed.     

Synthesis of single-walled carbon nanotubes in mesoporous silica film and their field emission property

We have succeeded in direct synthesis of single-walled carbon nanotubes (SWNTs) on a conductive substrate coated with a 3D mesoporous silica film, and observed the field emission. Co catalysts for the growth of SWNTs are deposited on the substrate by electroplating. The particle size of the catalyst is well-controlled inside defined space of the mesoporous silica film. Furthermore, the location of Co particles can be controlled in the mesopores by the electroplating method. Mono-dispersed SWNTs are grown along with the mesopores that are normal to the substrate, because Co particles are deposited at the bottom of the mesopores. It is also found that the mesoporous silica film prevents the aggregation of Co catalysts and the distortion of Au layer as the conductive substrate. The field emission measurement shows that the turn-on field is 4.2 V/μm at 10 μA/cm². The field enhancement factor is about 1500. This approach provides an efficient methodology for fabricating an SWNTs-based field emitters. PACS 73.63.Fg; 78.55.Mb     

Synthesis and photoluminescence properties of ZnO nanorods and nanotubes

Different morphologies of zinc oxide (ZnO) nanorods and nanotubes, which were grown under the same conditions but different dissolving processes, are prepared in our experiment through hydrothermal method. After the growth process, cooling down the reactor naturally or dissolving at a constant temperature of 40 °C, preferential dissolution will occur at different places on the tip of ZnO nanorods. During the dissolution process, different dissolution rates on the entire surface of nanorod will lead to different nanostructures. ZnO nanorods and nanotubes on Cu substrates display the same PL property with strong green emission but weak UV emission, while ZnO nanorods on Si substrates exhibits a relatively strong UV emission.     

Photoluminescence and field emission properties of Sn-doped ZnO microrods

Sn-doped ZnO (SZO) microrods have been fabricated by a thermal evaporation method. Effect of Sn dopant on the microstructure, morphological and composition of as-prepared SZO microrods have been investigated by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The influence of the doping concentration on the morphological of the microrods has been investigated. Photoluminescence (PL) of these SZO microrods exhibits a weak ultraviolet (UV) emission peak at around 382 nm and the strong green emission peak at around 525 nm at room temperature. Field emission measurements demonstrate that the SZO possess good performance with a turn-on field of ∼1.94 V/μm and a threshold field of ∼3.23 V/μm, which have promising application as a competitive cathode material in FE microelectronic devices.     

Electron field emission properties of closed carbon nanotubes

Recent experiments have shown that carbon nanotubes exhibit excellent electron field emisson properties with high current densities at low electric fields. Here we present theoretical investigations that incorporate geometrical effects and the electronic structure of nanotubes. The electric field is dramatically enhanced near the cap of a nanotube with a large variation of local field distribution. It is found that deviation from linear Fowler-Nordheim behavior occurs due to the variation of the local field in the electron tunneling region. The maximum current per tube is of the order of 10 microA. Local and microscopic aspects of field emission from nanotubes are also presented.     

Thermal instability of field emission from carbon nanotubes

The mechanism that limits the emission current of a carbon-nanotube-based cathode due to the temperature dependence of the emissivity of the nanotube is studied. This limitation has the character of thermal instability that shows up as an infinite increase in the emitter temperature after a certain emission current is exceeded. The heat conduction equation is solved for a nanotube at various model temperature dependences of the thermal and electrical conductivities of the nanotube in order to derive the limiting emission current as a function of the electrical conductivity of the nanotube.     

Mechanism of field electron emission from carbon nanotubes

Field electron emission (FE) is a quantum tunneling process in which electrons are injected from materials (usually metals) into a vacuum under the influence of an applied electric field. In order to obtain usable electron current, the conventional way is to increase the local field at the surface of an emitter. For a plane metal emitter with a typical work function of 5 eV, an applied field of over 1 000 V/μm is needed to obtain a significant current. The high working field (and/or the voltage between the electrodes) has been the bottleneck for many applications of the FE technique. Since the 1960s, enormous effort has been devoted to reduce the working macroscopic field (voltage). A widely adopted idea is to sharpen the emitters to get a large surface field enhancement. The materials of emitters should have good electronic conductivity, high melting points, good chemical inertness, and high mechanical stiffness. Carbon nanotubes (CNTs) are built with such needed properties. As a quasi-one-dimensional material, the CNT is expected to have a large surface field enhancement factor. The experiments have proved the excellent FE performance of CNTs. The turn-on field (the macroscopic field for obtaining a density of 10 μA/cm²) of CNT based emitters can be as low as 1 V/μm. However, this turn-on field is too good to be explained by conventional theory. There are other observations, such as the non-linear Fowler-Nordheim plot and multi-peaks field emission energy distribution spectra, indicating that the field enhancement is not the only story in the FE of CNTs. Since the discovery of CNTs, people have employed more serious quantum mechanical methods, including the electronic band theory, tight-binding theory, scattering theory and density function theory, to investigate FE of CNTs. A few theoretical models have been developed at the same time. The multi-walled carbon nanotubes (MWCNTs) should be assembled with a sharp metal needle of nano-scale radius, for which the FE mechanism is more or less clear. Although MWCNTs are more common in present FE applications, the single-walled carbon nanotubes (SWCNTs) are more interesting in the theoretical point of view since the SWCNTs have unique atomic structures and electronic properties. It would be very interesting if people can predict the behavior of the well-defined SWCNTs quantitatively (for MWCNTs, this is currently impossible). The FE as a tunneling process is sensitive to the apex-vacuum potential barrier of CNTs. On the other hand, the barrier could be significantly altered by the redistribution of excessive charges in the micrometer long SWCNTs, which have only one layer of carbon atoms. Therefore, the conventional theories based upon the hypothesis of fixed potential (work function) would not be valid in this quasi-one-dimensional system. In this review, we shall focus on the mechanism that would be responsible for the superior field emission characteristics of CNTs. We shall introduce a multi-scale simulation algorithm that deals with the entire carbon nanotube as well as the substrate as a whole. The simulation for (5, 5) capped SWCNTs with lengths in the order of micrometers is given as an example. The results show that the field dependence of the apex-vacuum electron potential barrier of a long carbon nanotube is a more pronounced effect, besides the local field enhancement phenomenon.     

Field emission from multi-walled carbon nanotubes and its application to electron tubes

Received: 5 December 1997     

锥顶碳纳米管的结构稳定性与场致发射性能

运用密度泛函理论研究了锥顶碳纳米管的结构稳定性与电子场致发射性能.结果表明:在外电场作用下,该体系的结构稳定性明显优于碳纳米锥体、C₃₀半球封口的碳纳米管,且电子发射性能与锥角大小、锥顶构型密切相关,特别是锥角38.9°及棱脊型顶部的cone₁@(6,6)综合性能最优,用其作为场致发射源的阴极时可显著提高发射电流密度并延长器件的使用寿命. 关键词： 锥顶碳纳米管 电子场致发射 结构稳定性 密度泛函理论     

ZnO nanotubes: Controllable synthesis and tunable UV emission modulated by the wall thickness

The ZnO nanotubes (ZNTs) with different wall thickness were fabricated by a simple wet chemical approach. Both indirect and direct transitions contribute to the UV emission of ZNTs. With the decrease of wall thickness, not only the indirect transition becomes more and more important during the emission process due to the stronger surface band bending effects and even turns into the main emission when the wall thickness decreases to 25 nm, but also the PL intensity is enhanced step by step due to the less defect density and higher carrier concentration caused by the introduction of chlorine in ZNTs during the etching process.     

Enhanced near-band-edge emission and field emission properties from plasma treated ZnO nanowires

Near-band-edge emission in photoluminescence of ZnO nanowires was found to be significantly improved after plasma treatment. The ratio of ultraviolet emission peak intensity before and after plasma treatment is as high as 3.5. Field emission properties were considerably enhanced after plasma treatment as well. Current emission density has been increased two orders of magnitude under the same electric field. Passivation of surface states and surface morphology change were found to be responsible for such an effective improvement. Our results suggest that the plasma treatment method is effective in enhancing both the near-band-edge emission in photoluminescence and field electron emission performance from ZnO nanowires.     

Light emission from carbon nanofilaments/nanotubes at field electron emission

The spatial distribution of light emission has been studied in planar field electron emitters with long and sparse carbon nanofilaments/nanotubes. The photographic recording of light emission of the emitting nanofilaments/nanotubes is shown to be efficient to determine the position of individual nanofilaments/ nanotubes in different emitter surface areas, as well as to highlight the nanofilaments/nanotube agglomerate distribution over the emitter surface, which mainly contributes to its emission.     

碳纳米管场致电子发射新机制

基于对长达 1μm的 (5 ,5 )碳纳米管的量子力学计算 ,作者发现使碳纳米管具有优异场致电子发射特性的因素除了人们预期的尖端场增强之外 ,电荷在纳米管尖端的积累造成有效功函数 (真空势垒 )的非线性下降也起了非常重要的作用 .对外加电场Vappl=10— 14V/ μm下的碳纳米管进行了计算 ,得到与实验结果相近的发射电流