Field emission properties of RuO2 thin film coated on carbon nanotubes

Carbon nanotubes (CNTs) have been widely applied in field emission (FE) due to their high geometric aspect ratio and low work function. More recently, researchers have introduced ruthenium dioxide (RuO₂) as a field emitter because of its excellent chemical and thermal stability due to its oxide nature. This study used the surface morphology of CNTs and the field emission (FE) stability of RuO₂ to improve FE characteristics. Since the work functions of CNTs and RuO₂ are very close, this study combined these two elements by applying a thin film of RuO₂ on the CNT surface. In the process of covering the tips of CNTs with a thin film of RuO₂ eventually obtained the best matching of these two elements. The study not only enhanced the FE performance of CNTs but also extended FE lifetime by applying a thin film of RuO₂ on the CNT tips.     

Clean carbon nanotube field emitters aligned horizontally

Horizontally aligned carbon nanotube (CNT) field emitters, which strongly adhere to the substrate and show good field emission properties, were fabricated by electrophoresis deposition and fissure formation techniques. A thin film of CNTs was deposited on a substrate, by electrophoresis, from an aqueous mixture of CNT and detergent, and then the detergent was deposited also by electropholysis. CNTs with a clean surface were exposed in the fissures produced by firing. The field emission was increased significantly due to the additional deposition of the detergent. When the CNTs were cut by increasing the firing time, the field emission increased significantly, while their stability decreased considerably. Our method does not require any further treatment for field emission.     

Enhanced Field Emission from a Carbon Nanotube Array Coated with a Hexagonal Boron Nitride Thin Film

A high‐quality field emission electron source made of a highly ordered array of carbon nanotubes (CNTs) coated with a thin film of hexagonal boron nitride (h‐BN) is fabricated using a simple and scalable method. This method offers the benefit of reproducibility, as well as the simplicity, safety, and low cost inherent in using B₂O₃ as the boron precursor. Results measured using h‐BN‐coated CNT arrays are compared with uncoated control arrays. The optimal thickness of the h‐BN film is found to be 3 nm. As a result of the incorporation of h‐BN, the turn‐on field is found to decrease from 4.11 to 1.36 V μm^?1, which can be explained by the significantly lower emission barrier that is achieved due to the negative electron affinity of h‐BN. Meanwhile, the total emission current is observed to increase from 1.6 to 3.7 mA, due to a mechanism that limits the self‐current of any individual emitting tip. This phenomenon also leads to improved emission stability and uniformity. In addition, the lifetime of the arrays is improved as well. The h‐BN‐coated CNT array‐based field emitters proposed in this work may open new paths for the development of future high‐performance vacuum electronic devices.     

Coating of carbon nanotubes with amorphous carbon nitride thin films and characterization of long-term emission stability

The effects of amorphous carbon nitride (CN) thin films that were coated on carbon nanotubes (CNTs) and their thermal treatment were investigated, in terms of the chemical bonding and morphologies of the CNTs and their field emission properties. CNTs were directly grown on conical tip-type tungsten substrates via the inductively coupled plasma-chemical vapor deposition (ICP-CVD) system, and the CNTs were coated with CN films using the RF magnetron sputtering system. The CN-coated CNTs were thermally treated using the rapid thermal annealing (RTA) system by varying the temperature (300-700 °C). The morphologies, microstructures, and chemical compositions of the CN-coated CNTs were analyzed as a function of the thickness of the CN layers and the RTA temperatures. The field emission properties of the CN/CNT hetero-structured emitters, and the fluctuation and long-term stability of the emission currents were measured and compared with those of the conventional non-coated CNT-emitter. The results showed that the electron emission capability of CNT was noticeably improved by coating a thin CN layer on the surface of the CNT. This was attributed to the low work function and negative electron affinity nature of the CN film. The CN-coated CNT-emitter had a more stable emission characteristic than that of the non-coated one. In addition, the long-term emission stability of the CN-coated emitter was further enhanced by thermal treatment, which was verified by x-ray photoelectron spectroscopy (XPS) analysis.     

Electron-emission properties of carbon nanotube micro-tips coated by amorphous carbon nitride films

An approach to the preparation of a tip-type of field emitter that is made up of carbon nanotubes (CNTs) coated with amorphous carbon nitride (a-CN_x) films is presented for the purpose of enhancing its electron emission property. CNTs were directly grown on nano-sized conical-type tungsten tips via the inductively coupled plasma-chemical vapor deposition system, and a-CN_x films were coated on the CNTs using an radio frequency magnetron sputtering system. The morphologies and microstructures of the a-CN_x-coated CNTs were analyzed via field emission scanning electron microscopy, energy-dispersive x-ray spectroscopy, high-resolution transmission electron microscopy, and x-ray photoelectron spectroscopy. The electron emission properties of the a-CN_x/CNT hetero-structures were measured using a high-vacuum field emission measurement system. The best field emission properties, such as a very low turn-on voltage of 500 V and a maximum emission current of 176 μA were achieved for the CNT emitter coated with the 5 nm-thick a-CN_x film. In addition, this emitter showed a highly stable behavior in long-term (up to 25 h) electron emission.     

Effects of welding head on the carbon nanotube field emission in ultrasonic nanowelding

Ultrasonic nanowelding technique was used to improve the field emission properties of carbon nanotube (CNT) cathodes. Two kinds of welding heads were used and the effects of the head on the emission properties were studied. The results show that cathodes welded by Al₂O₃ flat head demonstrate excellent field emission properties with high emission current density and good current stability. The improved field emission performance is attributed to the reliable and low resistance contact between CNTs and metal substrates. Cathodes welded by steel matrix head show a lower turn-on electric field due to the protruding CNTs at the edge of the welded pits.     

Effective electron emitters by molybdenum oxide-coated carbon nanotubes core–shell nanostructures

In this article, we showed that simple metal oxide coatings such as MoO₃ can be an effective enhancer for carbon nanotubes (CNTs) in field emission (FE) performance. For comparison, the FE properties of the pristine vertically aligned multi-walled CNTs with the metal oxide-coated CNTs were investigated. The metal oxide coating of the pristine CNTs was carried out by metal–organic chemical vapor deposition (MOCVD) method at 400 °C using Mo(CO)₆ as the precursor. The core–shell structure of the nanocomposite was studied by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) results showed that the surface of the coating material was mainly MoO₃. FE test indicated that the MoO₃-coated CNTs film exhibited an enhanced performance than the pristine CNTs with a turn-on field of 1.33 V μm⁻¹ and a field enhancement factor β estimated to be ~7000. Ultraviolet photoelectron spectroscopy (UPS) results confirmed a lower electron emission barrier height for MoO₃-coated CNTs than for the pristine CNTs. The mechanism of the enhanced FE performance is discussed based on Schottky barrier effect.     

Enhanced field emission characteristics of nitrogen-doped carbon nanotube films grown by microwave plasma enhanced chemical vapor deposition process

Nitrogen-doped carbon nanotube (CNT) films have been synthesized by simple microwave plasma enhanced chemical vapor deposition technique. The morphology and structures were investigated by scanning electron microscopy and high resolution transmission electron microscopy. Morphology of the films was found to be greatly affected by the nature of the substrates. Vertically aligned CNTs were observed on mirror polished Si substrates. On the other hand, randomly oriented flower like morphology of CNTs was found on mechanically polished ones. All the CNTs were found to have bamboo structure with very sharp tips. These films showed very good field emission characteristics with threshold field in the range of 2.65-3.55 V/μm. CNT film with flower like morphology showed lower threshold field as compared to vertically aligned structures. Open graphite edges on the side surface of the bamboo-shaped CNT are suggested to enhance the field emission characteristics which may act as additional emission sites.     

Influence of the concentration of carbon nanotubes on electrical conductivity of magnetically aligned MWCNT–polypyrrole composites

The goal of this work is to study the effect of high magnetic pulses on electrical property of carbon nanotube–polypyrrole (CNT–PPy) composites with different CNT concentrations. CNT–PPy composites are produced in fractions of 1, 5 and 9 wt%. During the polymerization process, the CNTs are homogeneously dispersed throughout the polymer matrix in an ultrasonic bath. Nanocomposite rods are prepared. After exposure to 30 magnetic pulses, the resistivity of the rods is measured. The surface conductivity of thin tablets of composites is studied by 4-probe technique. The magnitude of the pulsed magnetic field is 10 Tesla with time duration of 1.5 ms. The results show that after applying 30 magnetic pulses, the electrical resistivity of the composites decreases depending on the concentration of CNTs in the composites. The orientation of CNTs is probed by atomic force microscopy (AFM) technique. AFM images approved alignment of CNT–polymer fibres in the magnetic field. We found that the enhancement in the electrical properties of CNT–PPy composites is due to rearrangement and alignment of CNTs in a high magnetic field. The stability of nano-composites is studied by Fourier transform infrared spectroscopy.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Preparation and tribological properties of novel carbon nanotube self-assembled composite films

Carbon nanotube (CNT) composite thin films were prepared on a single-crystal silicon substrate by a self-assembling process from a specially formulated solution. Rare earth solution (RES) surface modification and appropriate acid-treatment methods were used to functionalise carbon nanotubes (CNTs). Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared first. The terminal thiol groups (–SH) in the film was oxidised to sulphonic acid groups (–SO₃H) in situ to enhance the film with good chemisorption ability. Treated Caron nanotubes were deposited on the oxidised MPTS–SAM by means of chemisorption with the SO₃H group. The surface energy, chemical composition, phase transformation and surface morphology of the films were analysed using contact angle measurements, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy. As a result, a conclusion could be made that some lanthanum elements react with –SO₃H groups on the surface of the substrate by a chemical bond, which will improve the bonding strength between the films and the CNTs. Since the CNT thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).     

Photolithographic fabrication of gated self-aligned parallel electron beam emitters with a single-stranded carbon nanotube

In this paper we report on the development of a photolithographic process to fabricate a gated-emitter array with single-stranded carbon nanotubes (CNTs) self-aligned to the center of the emitter gate using plasma-enhanced chemical vapor deposition (PECVD). Si tips are formed on a silicon wafer by anisotropic etching of Si using SiO(2) as a mask. Deposition of a SiO(2) insulating layer and Cr-W electrode layers creates protrusions above the Si tips. This wafer is polished, and the Cr-W on the tips is removed. Etching of the SiO(2) using hydrofluoric acid is performed to expose the gated Si tip. Incorporation of a novel diffusion process produces single-stranded CNTs by depositing a thin Ni layer on the Si tips and thermally diffusing the Ni layer to yield a catalyst particle for single-stranded CNT growth. The large surface to volume ratio at the apex of the Si tip allows a Ni particle to remain to act as a catalyst to grow a single-stranded CNT for fabricating the CNT based emitter structure. Diffusion of the Ni is carried out in situ during the heating phase of the PECVD CNT growth process at 600?°C. The diameters of the observed CNTs are on the order of 20?nm. The field emission characteristics of the gated field emitters are evaluated. The measured turn-on voltage of the gated emitter is 5?V.     

Effects of Supercritical Fluids Activation on Carbon Nanotube Field Emitters

This paper proposes a novel method to enhance the emission characteristics of carbon nanotubes (CNTs). It is extremely possible for CNTs to adsorb moisture and other contaminants during the fabrication processes, leading to the degraded field emission characteristics. In this work, CNT emitters are activated with commonly used heating process and supercritical carbon dioxide (SCCO₂) fluids technology for removing adsorbed residue moisture. Experimental results have demonstrated that the electrical stability and field emission enhancement of CNT emitters are effectively achieved by the SCCO₂ fluids treatment compared to the heating process, due to the minimization of residuary moisture in CNTs     

Robust and Aligned Carbon Nanotube/Titania Core/Shell Films for Flexible TCO‐Free Photoelectrodes

Carbon nanotube (CNT)/semiconducting oxide hybrids are an ideal architecture for light‐harvesting devices, in which the CNTs are expected to not only act as a scaffold but also provide fast transport paths for photogenerated charges in the oxide. However, the current potential of CNTs for charge transport is largely suppressed due to the nanotubes not being interconnected but isolated by the low conductive oxide coatings. Herein, a flexible and conductive CNT/TiO₂ core/shell heterostructure film is reported, with aligned and interconnected CNTs wrapped in a continuous TiO₂ coating. Without using additional transparent conducting oxide (TCO) substrates, this unique feature of the film boosts the incident photon‐to‐electron conversion efficiency to 32%, outperforming TiO₂ nanoparticle electrodes fabricated on TCO substrates. Moreover, the film shows high structural stability and can generate a stable photocurrent even after being bent hundreds of times.     

Optimization of field emission properties of carbon nanotubes by Taguchi method

It is the purpose of this study to evaluate the field emission property of carbon nanotubes (CNTs) prepared by microwave plasma-enhanced chemical vapor deposition (MPCVD) method. Nickel layer of 5 nm in thickness on 20-nm thickness titanium nitride film was transformed into discrete islands after hydrogen plasma pretreatment. CNTs were then grown up on Ni-coated areas by MPCVD. Through the practice of Taguchi method, superior CNT films with very low emission onset electric field, about 0.7 V/μm (at J = 10 μA/cm²), are attained without post-deposition treatment. It is found that microwave power has the most important influence on the field emission characteristics of CNT films. The increase of methane flow ratio will downgrade the degree of graphitization of CNT and thus its field emission characteristics. Scanning electron microscope and transmission electron microscopy (TEM) observation and energy dispersive X-ray spectrometer analysis reveal that CNT growth by MPCVD is based on tip-growth mechanism. TEM micrographs validate the hollow, bamboo-like structure of the multi-walled CNTs.     

Preparation, characterization and anion exchange properties of polypyrrole/carbon nanotube nanocomposites

In this study, polypyrrole (PPy) thin films were electrodeposited on carbon nanotube (CNT) backbones by applying a constant deposition potential in 0.1 M pyrrole solution with different electrolytes, such as NaCl, NaNO3, or NaClO4. The hybrid films were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy, and cyclic voltammetry. SEM images revealed the nanostructrure of PPy films generated on CNT surface. The electrochemical and anion exchange properties of the PPy-CNT composite films have been investigated. Nanostructured composite thin films of PPy-CNTs were studied by cyclic voltammetry between 0.4 and -0.8 V in aqueous solution to evaluate their cycling stability and capacity for electrically switched anion exchange. The presence of the CNT backbone greatly improved the anion exchange capacity and stability of the PPy-CNT composite film, which may be attributed to the high surface area of CNT matrix, nanostructure of the PPy film, and the interaction between CNTs and PPy.     

Carbon Nanotubes for Cold Electron Sources

Technological advances in the field of microelectronic fabrication techniques have triggered a great interest in vacuum microelectronics. In contrast to solid‐state microelectronics, which entails scattering‐dominated electron transport in semiconducting solids, vacuum microelectronics relies on the scattering‐free, ballistic motion of electrons in vacuum. Since the first international conference on vacuum microelectronics substantial progress in this field has been made. The first technological devices using micrometer‐sized electron emitting structures are currently being commercialized. Field‐emission flat‐panel displays (FED) seem to be an especially promising competitor to LCD displays. Today there is only one mature technology for producing micro‐gated field‐emission arrays: the Spindt metal‐tip process. The drawbacks of this technology are expensive production, critical lifetime in vacuum, and high operating voltage. Carbon nanotubes (CNT) can be regarded as the potential second‐generation technology to the Spindt metal micro‐tip. In this review we show that the field emission (FE) behavior of CNT can be accurately described by Fowler–Nordheim tunneling and that the field‐enhancement factor β is the most prominent factor. Therefore the FE properties of a CNT thin film can be understood in terms of local field enhancement β(x,y), which can be determined with scanning anode field emission microscopy (SAFEM). To characterize the FE properties of an ensemble of electron emitters we used a statistical approach (as for thin film emitters), where f(β)dβ gives the number of emitters on a unit area with field‐enhancement factors within the interval [β,β + dβ]. We show that the field‐enhancement distribution function f(β) gives an almost complete characterization of the FE properties.     

纳米金刚石掺混对碳纳米管薄膜场发射性能的影响

为了提高碳纳米管（CNT）阴极膜的场发射均匀性和稳定性,同时改善CNT膜的制作过程,本文提出一种掺混纳米金刚石（D）制作高性能丝网印刷CNT膜的方法．通过掺混碳相纳米金刚石,形成结构匹配的CNT／D复合膜,CNT膜内的间隙势垒减少,发射体分散更均匀,膜层与基底接触面积增加;同时,结合纳米金刚石的负电亲和势和场发射特性,可有效提高CNT阴极膜的导电性,增大有效发射体的密度．场发射特性测试表明CNT／D复合膜能得到1．89V／μm的低开启电场,在2．8V／μm场强下,场发射电流密度远高于普通CNT膜,达到463μA／cm2,与普通CNT阴极膜相比,CNT／D复合膜的场发射稳定性显著提高,在400℃热处理后CNT／D膜激发阳极发光更均匀．     

Aligning Solution‐Derived Carbon Nanotube Film with Full Surface Coverage for High‐Performance Electronics Applications

The main challenge for application of solution‐derived carbon nanotubes (CNTs) in high performance field‐effect transistor (FET) is how to align CNTs into an array with high density and full surface coverage. A directional shrinking transfer method is developed to realize high density aligned array based on randomly orientated CNT network film. Through transferring a solution‐derived CNT network film onto a stretched retractable film followed by a shrinking process, alignment degree and density of CNT film increase with the shrinking multiple. The quadruply shrunk CNT films present well alignment, which is identified by the polarized Raman spectroscopy and electrical transport measurements. Based on the high quality and high density aligned CNT array, the fabricated FETs with channel length of 300 nm present ultrahigh performance including on‐state current I_on of 290 µA µm^?1 (V_ds = ?1.5 V and V_gs = ?2 V) and peak transconductance g_m of 150 µS µm^?1, which are, respectively, among the highest corresponding values in the reported CNT array FETs. High quality and high semiconducting purity CNT arrays with high density and full coverage obtained through this method promote the development of high performance CNT‐based electronics.     

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).