Field emission properties of electrodeposited cobalt nanowire arrays grown in anodic aluminum oxide

The excellent vertically aligned cobalt nanowire arrays were electrodeposited into anodic aluminum oxide (AAO) templates. Each nanowire has the same length with 20 μm and the diameter with 60 nm. The field emission characteristics of the nanowires were firstly studied based on current-voltage measurements and the Fowler-Nordheim equation. The electron field emission measurements on the samples showed a turn-on field (1 mA/cm²) of 1.66 V/μm, a field enhancement factor of β = 3054 and a current density of 600 mA/cm² at a relatively low voltage of 4.3 V/μm. The nanowire arrays could be an ideal alternative to carbon nanotubes and ZnO nanowires for the fabrication of flat panel displays.     

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.     

Synthesis of large-area single-walled carbon nanotube films on glass substrate and their field electron emission properties

Large-area and homogeneous single-walled carbon nanotube (SWCNT) films have been deposited via arc discharge directly on glass substrate coated with a layer of indium tin oxide film. The characterization, by means of electron microscopy and Raman spectroscopy, shows that the as-grown films are uniformly woven and consist of SWCNT with diameters ranging from 0.82 to 1.15 nm. As a cathode material, the field emission test indicates the films have low turn-on field of ∼1.2 V/μm at 10 μA/cm² emission current, and high emission intensity causing luminance of about 7000 cd/cm² with fine uniformity. The best performing sample exhibits a constant degradation of less than 3% per hour at an emission current of around 1 mA. Measuring with the high voltage (2000 V) on the films for 2.0 h increased the field enhancement factor from 4500 to 5400 at the high field region. The results are of significance to the development of field emission display using nanoemitters.     

Fabrication of carbon nanoflakes by RF sputtering for field emission applications

In this paper, an ultra thin sheet-like carbon nanostructure, carbon nanoflake (CNF), has been effectively fabricated by RF sputtering on Si substrate without any catalyst or special substrate pre-treatment. The CNFs were chosen to be the field emission emitters because of their very sharp and thin edges which are potentially good electron field emission sites. The effect of deposition parameters such as substrate temperature, gas flow ratio and RF power on the field emission properties is discussed in detail. The sheet-like structures with thickness of about 10 nm or less stand on edge on the substrate and have a defective graphite structure. The field emission properties of the sample deposited at the optimum deposition conditions are turn-on field of 5.5 V/μm and current density of 1.4 mA/cm² at 11 V/μm. Considering the inexpensive manufacturing cost, lower synthesis temperature and ease of large-area preparation, the CNFs with low turn-on field deposited by RF sputtering might have a potential application in field emission devices.     

Preparation and electrochemical properties of multiwalled carbon nanotubes-nickel oxide porous composite for supercapacitors

Porous nickel oxide/multiwalled carbon nanotubes (NiO/MWNTs) composite material was synthesized using sodium dodecyl phenyl sulfate as a soft template and urea as hydrolysis-controlling agent. Scanning electron microscopy (SEM) results show that the as-prepared nickel oxide nanoflakes aggregate to form a submicron ball shape with a porous structure, and the MWNTs with entangled and cross-linked morphology are well dispersed in the porous nickel oxide. The composite shows an excellent cycle performance at a high current of 2 A g⁻¹ and keeps a capacitance retention of about 89% over 200 charge/discharge cycles. A specific capacitance approximate to 206 F g⁻¹ has been achieved with NiO/MWNTs (10 wt.%) in 2 M KOH electrolyte. The electrical conductivity and the active sites for redox reaction of nickel oxide are significantly improved due to the connection of nickel nanoflakes by the long entangled MWNTs.     

Efficient field emission properties of ZnO (core)/graphite (shell) nanowires

In this work the field emission studies of a new type of field emitter, zinc oxide (ZnO) core/graphitic (g-C) shell nanowires are presented. The nanowires are synthesized by chemical vapor deposition of zinc acetate at 1300 °C Scanning and transmission electron microscopy characterization confirm high aspect ratio and novel core–shell morphology of the nanowires. Raman spectrum of the nanowires mat represents the characteristic Raman modes from g-C shell as well as from the ZnO core. A low turn on field of 2.75 V/μm and a high current density of 1.0 mA/cm² at 4.5 V/μm for ZnO/g-C nanowires ensure the superior field emission behavior compared to the bare ZnO nanowires.     

High-aligned carbon nanotube film with netlike bulges

High-aligned carbon nanotubes film with netlike bulges made of catalyst particles has been synthesized on a silica wafer by pyrolyzing ferrocene/melamine mixtures. The structure and composition of carbon nanotubes are investigated by scanning electron microscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electron energy-loss spectroscopy (EELS). It is found that these nanotubes have uniform outer diameters of about 25 nm and lengths of about 40 μm. High-resolution TEM images show that each carbon nanotube is composed of graphite-like layers arranged in a stacked-cup-like structure. XPS spectrum shows that the crust covering the tops of the aligned carbon nanotube film consists of carbon, iron and ferric oxide. The EELS spectrum shows that these nanotubes are pure-carbon tubes. The formation mechanism of the netlike bulges has been provided.     

Fabrication of multi-emitter array of CNT for enhancement of current density

We studied and compared field emission properties of two kinds of emitters of randomly oriented multi-wall carbon nanotubes (MWNTs), viz. continuous film emitter (CFE) and multi-emitter array (MEA). The CFE has a continuous film of MWNTs while the MEA consists of many equidistant small circular emitters. Both types of emitters were prepared by dispersing MWNTs over a titanium (Ti) film (for CFEs) or Ti circular islands (for MEAs) deposited on tantalum (Ta) followed by rooting of MWNTs into the Ti film or the Ti islands at high temperature. Emission properties of both types of emitters were analyzed with changing their emission areas. In case of the CFEs, current density decreased with an increase in emission area whereas consistent current densities were achieved from MEAs with different emission areas. In other words, the total emission current was achieved in proportion to the emission area in the case of MEAs. Additionally a high current density of 22 A/cm² was achieved at an electric field of 8 V/μm from MEAs, which was far better than that obtained from CFEs. The high current density in MEAs was attributed to edge effect, in which higher emission current is achieved from the edge of film emitter. The results indicate that the field emission characteristics can be greatly improved if a cathode contains many small equidistant circular emitters instead of a continuous film. The outstanding stability of the CFE and the MEA has been demonstrated for 2100 and 1007 h, respectively.     

HRTEM observations on composites of tin and tin dioxide nanoparticles dispersed on carbon nanotubes by single-atoms-to-clusters method

Nano-composites of tin and tin dioxide particles were synthesized on carbon nanotubes by the single-atoms-to-clusters (SAC) method, and their structures were investigated by high-resolution transmission electron microscopy. By changing the heat-treatment temperature during the SAC process, two different types of samples were obtained. The samples prepared around 450 K were aggregates of 2-4 nm-sized tin dioxide nanoparticles, and their size distributions on carbon nanotubes are in the range 20-40 nm. The other samples formed above 600 K had a core-shell structure of diameter 20-40 nm. The core and shell were made of tin single crystal and disordered oxidized tin, respectively. The thickness of the oxidized layers was ca. 4 nm.     

Effects of the size of nano-copper catalysts and reaction temperature on the morphology of carbon fibers

In this study, carbon fibers with different morphologies, including coiled carbon nanofibers and straight carbon fibers, were obtained by the chemical vapor deposition using a Cu-catalytic pyrolysis of acetylene at 250 °C. The influences of nano-copper catalyst particle size and the reaction temperature on the morphology of carbon fibers were investigated. Under the same reaction condition, coiled carbon nanofibers generally were synthesized using nano-copper catalyst with smaller particles size, and bigger copper particles are apt to produce straight carbon fibers. With decreasing of reaction temperature to 200 °C, straight carbon fibers were obtained, instead of coiled carbon nanofibers at 250 °C. The product was characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD).     

Cadmium sulfide nanotubes thin films: Characterization and photoelectrochemical behavior

Monodisperse cadmium sulfide nanotubes (CdS NTs) with a diameter of 100 nm were synthesized on indium-doped tin oxide glass substrates using chemical bath deposition and self-sacrificial template technique. This CdS thin film was characterized by transmission electron microscope, scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis spectrophotometer. This film gave a short circuit photocurrent of 4.4 mA/cm², an open circuit photovoltage of 0.75 V, a fill factor of 0.49, and an overall conversion efficiency of 1.29% under a simulated solar illumination of 100 mW/cm². All these photoelectrochemical properties of the films were dependent on the microstructure of the nanotubes and the thickness of the film. A facile and efficient way to prepare CdS-based photoelectrodes for photoelectrochemical cells was provided in this report.     

Hydrothermal synthesis, characterization, photocatalytic activity and dye-sensitized solar cell performance of mesoporous anatase TiO2 nanopowders

Mesoporous anatase TiO₂ nanopowder was synthesized by hydrothermal method at 130 °C for 12 h. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), HRTEM, and Brunauer-Emmett-Teller (BET) surface area. The as-synthesized sample with narrow pore size distribution had average pore diameter about 3-4 nm. The specific BET surface area of the as-synthesized sample was about 193 m²/g. Mesoporous anatase TiO₂ nanopowders (prepared by this study) showed higher photocatalytic activity than the nanorods TiO₂, nanofibers TiO₂ mesoporous TiO₂, and commercial TiO₂ nanoparticles (P-25, JRC-01, and JRC-03). The solar energy conversion efficiency (η) of the cell using the mesoporous anatase TiO₂ was about 6.30% with the short-circuit current density (Jsc) of 13.28 mA/cm², the open-circuit voltage (Voc) of 0.702 V and the fill factor (ff) of 0.676; while η of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm², Voc of 0.704 V and ff of 0.649.     

Fabrication of carbon nanoneedle and carbon nanowall mixture film with two-step growth method

A novel nano-carbon electron emitter film has been developed on a stainless steel substrate by a direct current plasma chemical vapor deposition system. Samples grown at temperatures of 900 °C and 1100 °C showed different surface morphologies. It is found that a two-step growth process established by combining these two temperature growths together is suitable for deposition of a high density emitter array film. The as-grown nano-carbon film indicates a carbon nanoneedle and carbon nanowall mixture film, where the needle array density is about 3 × 10⁷/cm². The I-V characteristic shows an emission current density of 228 mA/cm² at 2.5 V/μm, and the field emission current is stable, making it possibly suitable for developing field emission devices.     

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.     

Physical properties of multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWNTs), which were prepared by hydrogen arc discharge, were purified by using an infrared radiation heating system. The morphology, structure, vibrational modes and crystalline perfection of purified MWNTs were investigated by using scanning electron microscopy, high-resolution transmission electron microscopy, an X-ray diffractometer and a Raman spectrometer. Moreover, the electrical conductivity of individual purified MWNTs was measured using a two-probe method using a micro manipulator system. It turned out that the MWNTs had a high degree of graphitization, an electrical conductivity of about 1.85×10³ S cm⁻¹ along the long axis, and an enormous current density of more than 10⁷ A cm⁻².     

Low temperature synthesis of Fe3O4 nanoparticles and its application in lithium ion batteries

Well dispersed Fe₃O₄ nanoparticles with mean size about 160 nm are synthesized by a simple chemical method at atmosphere pressure. The products are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and Raman spectrum. Electrochemical properties of the as-synthesized Fe₃O₄ nanoparticles as anode electrodes of lithium ion batteries are studied by conventional charge/discharge tests, showing initial discharge and charge capacities of 1140 mAh g⁻¹ and 1038 mAh g⁻¹ at a current density of 0.1 mA cm⁻². The charge and discharge capacities of Fe₃O₄ electrode decrease along with the increase of cycle number, arriving at minimum values near the 70th cycle. After that, the discharge and charge capacities of Fe₃O₄ electrode begin to increase along with the increase of cycle number, arriving at 791 and 799 mAh g⁻¹ after 393 cycles. The morphology and size of the electrode after charge and discharge tests are characterized by SEM, which exhibits a large number of dispersive particles with mean size about 150 nm.     

Growth of vertically aligned arrays of carbon nanotubes for high field emission

Vertically aligned multi-walled carbon nanotubes have been grown on Ni-coated silicon substrates, by using either direct current diode or triode plasma-enhanced chemical vapor deposition at low temperature (around 620 °C). Acetylene gas has been used as the carbon source while ammonia and hydrogen have been used for etching. However densely packed (∼ 10⁹ cm^− 2) CNTs were obtained when the pressure was ∼ 100 Pa. The alignment of nanotubes is a necessary, but not a sufficient condition in order to get an efficient electron emission: the growth of nanotubes should be controlled along regular arrays, in order to minimize the electrostatic interactions between them. So a three dimensional numerical simulation has been developed to calculate the local electric field in the vicinity of the tips for a finite square array of nanotubes and thus to calculate the maximum of the electron emission current density as a function of the spacing between nanotubes. Finally the triode plasma-enhanced process combined with pre-patterned catalyst films (using different lithography techniques) has been chosen in order to grow regular arrays of aligned CNTs with different pitches in the micrometer range. The comparison between the experimental and the simulation data permits to define the most efficient CNT-based electron field emitters.     

Synthesis,Structure and Field Emission of Carbon Nanotubes

Abstract

Multiwall and single-wall nanotubes were produced by carbon arc discharge in helium, and their structures were investigated by electron microscopy. Field emission from (1) as-grown multiwall nanotubes (MWNTs), (2) purified MWNTs and (3) purified single-wall nanotubes (SWNTs) was investigated by field emission microscopy. Of the three kinds of nanotubes studied, purified MWNTs whose tips are open provided the highest current at a fixed voltage. Although purified SWNTs provided the second highest current, SWNTs are not so robust as MWNTs against ion bombardment. As an application of nanotube field emitters, we manufactured cathode ray tube (CRT) lighting-elements by replacing conventional thermionic cathodes with nanotube field emitters. Stable electron emission, adequate luminance, and long life of the emitters were substantiated.     

Electron emission properties of CNT arrays grown with micro-molding in capillary (MIMIC) assisted process

We have selectively fabricated carbon nanotubes (CNTs) emitter arrays with a micro mold in capillary (MIMIC) assisted process. The electron emitter growth site was fabricated by resist patterning using the MIMIC process. The pattern was uniformly transferred to the substrate and well aligned CNTs were grown. The emitter produces a turn-on field of 2.7 V/μm with a field emission current of 10 μA/cm². The electron emission current can be controlled by emitter pattern width and pitch variation.     

Low temperature growth of carbon nanotubes in a magnetic field

We report on the growth of carbon nanotubes on a glass substrate at a low temperature of 450 °C by plasma-enhanced chemical vapor deposition in the presence of a magnetic field. The growth of carbon nanotubes can be realized at 450 °C only when a magnetic field is applied to the substrate. Carbon nanotubes cannot be grown in the absence of a magnetic field at the same temperature. An NH₃ plasma pretreatment significantly improved the uniformity of the grain size of the Ni catalyst under the magnetic field. The enhancement in the growth of CNTs at low temperature can be attributed to the magnetic moment pre-alignment of the ferromagnetic catalyst film under high magnetic field. A high emission current density of 20 mA/cm² was obtained at 6 V/μm and a stable emission current was observed. This method permits the growth of carbon nanotubes directly on glass substrate at much more reliable low temperatures for the fabrication of high-density field emitter arrays.