High-current field emission of point-type carbon nanotube emitters on Ni-coated metal wires

The fabrication and field emission characteristics are reported for point-type carbon nanotube (CNT) emitters formed by transferring a CNT film onto a Ni-coated Cu wire with a diameter of 1.24 mm. A Ni layer plays a role in enhancing the adhesion of CNTs to the substrate and improving their field emission characteristics. On firing at 400 °C, CNTs appear to directly bonded to a Ni layer. With a Ni layer introduced, a turn-on electric field of CNT emitters decreases from 1.73 to 0.81 V/μm by firing. The CNT film on the Ni-coated wire produces a high emission current density of 667 mA/cm² at quite a low electric field of 2.87 V/μm. This CNT film shows no degradation of emission current over 40 h for a current density of 60 mA/cm² at electric field of 6.7 V/μm. X-ray imaging of a printed circuit board with fine features is demonstrated by using our point-type CNT emitters.     

Stable and high current density electron emission using coniferous carbon nano-structured emitter

The electron emission properties of a coniferous carbon nano-structure (CCNS) based field emission electron gun have been measured. The CCNS was grown on a stainless steel substrate using chemical vapor deposition (CVD) and biased to about 50 kV. Stable, high-current-density electron emission (102 mA/cm²) was measured continuously for more than 1300 h. This result compares favorably to printed and directly grown carbon nanotube (CNT) based emitters. A wide range of potential applications are foreseen for CCNS based electron emitters, such as high intensity X-ray sources.     

High performance field emission of carbon nanotube film emitters with a triangular shape

We report novel two-dimensional (2D) shaped carbon nanotube (CNT) field emitters using triangular-shaped CNT films and their field emission properties. Using the 2D shaped CNT field emitters, we achieved remarkable field emission performance with a high emission current of 22 mA (equivalent to an emission current density >10⁵ A/cm²) and long-term emission stability at 1 mA for 20 h. We also discuss the field emission behavior of the 2D shaped CNT field emitter in detail.     

Surface properties of vertically aligned carbon nanotube arrays

This study focuses on the structural changes of vertically aligned carbon nanotube (CNT) arrays while measuring their adhesive properties and wetting behaviour. CNT forests grown by chemical vapor deposition with a height of ~ 100 µm, an outer CNT diameter of ~ 10 nm and a density of the order of ~ 10¹⁰ CNTs/cm² show an average adhesion of 4 N/cm² when pressed against a glass surface. The applied forces lead to the collapse of the regular CNT arrays which limits their reusability as functional dry adhesives. Goniometric water contact angle (CA) measurements on CNT forests show a systematic decrease from an initial value of ~ 126° to a final CA similar to highly orientated graphite. Environmental scanning electron microscopy shows that this loss of hydrophobicity is due to an evaporation induced compaction of CNTs together with the loss of their vertical alignment. We observe the formation of cellular patterns for controlled drying.     

Preparation and characterization of manganese oxide/CNT composites as supercapacitive materials

Manganese oxide was synthesized and dispersed on carbon nanotube (CNT) matrix by thermally decomposing manganese nitrates. CNTs used in this paper were grown directly on graphite disk by chemical vapor deposition technique. The capacitive behavior of manganese oxide/CNT composites was investigated by cyclic voltammetry and galvanostatic charge–discharge method in 1 M Na₂SO₄ aqueous solutions. When the loading mass of MnO₂ is 36.9 μg cm^− 2, the specific capacitance of manganese oxide/CNT composite (based on MnO₂) at the charge–discharge current density of 1 mA cm^− 2 equals 568 F g^− 1. Additionally, excellent charge–discharge cycle stability (ca. 88% value of specific capacitance remained after 2500 charge–discharge cycles) and power characteristics of the manganese oxide/CNT composite electrode can be observed. The effect of loading mass of MnO₂ on specific capacitance of the electrode has also been investigated.     

Packing density control of carbon nanotube emitters in an anodic aluminum oxide nano-template on a Si wafer

Carbon nanotubes (CNTs) emitters in the AAO templates on a silicon wafer were fabricated. The packing density of CNTs was changed in the order of 1 × 10⁷ − 7 × 10⁷ tips cm^− 2 depending upon the concentration of hydrogen in the reactant gas mixture. The emission current density was strongly dependent upon the packing density of the CNT emitters. Low turn-on fields of 1.6–2.1 V/μm and field enhancement factor of 1900–4970 were observed.     

Parametric study of intrinsic thermal transport in vertically aligned multi-walled carbon nanotubes using a laser flash technique

The thermal diffusivity of vertically aligned carbon nanotube (VACNT, multi-walled) films synthesized by thermal chemical vapor deposition was measured by a laser flash technique, and shown to be ～30 mm² s^?1 along the tube-alignment direction. The calculated thermal conductivities of the VACNT films and the individual CNTs were ～27 and ～540 W m^?1 K^?1, respectively. The technique was verified to be reliable although a proper sampling procedure is critical. A systematic parametric study of the effects of defects, buckling, tip-to-tip contacts, packing density, and tube–tube interaction on the thermal diffusivity was carried out. Defects and buckling decreased the thermal diffusivity dramatically. An increased packing density was beneficial in increasing the collective thermal conductivity of the VACNT film; however, the increased tube–tube interaction in dense VACNT films decreased the effective thermal conductivity of the individual CNTs in the films. The tip-to-tip contact resistance was shown to be ～1 × 10^?7 m² K W^?1. The study will shed light on the potential application of VACNTs as thermal interface materials in microelectronic packaging.     

Carbon nanotube/carbon nanofiber growth from industrial by-product gases on low- and high-alloy steels

The growth of carbon nanotubes (CNTs) on sheet metal surfaces (including low- and high-alloyed steel and Ni-plated steel) has been explored using a mixture of CO, CO₂, and H₂ as the precursor feedstock in a thermal chemical vapor deposition process. The influence of various experimental parameters such as the reactor temperature, reaction time, and precursor composition on the yield, purity, and dimensions of the CNTs has been elucidated. Addition of CO₂ during CNT growth leads to higher carbon deposition rates, especially for low- and high-alloyed steel. The diameters of the obtained CNTs range from 12 to 300 nm at carbon deposition rates of ～0.3 mg cm^?2 min^?1. The CNTs are observed to be uniformly distributed and adhered firmly to the substrates. The experimental conditions for CNT growth on sheet metal surfaces are very similar to concentrations and temperatures of a typical effluent stream of the steel industry. This process thus holds potential to harness waste gases to fabricate CNT-based coatings that impart added functionality to sheet metals, while further reducing the carbon footprint of steel plants.     

Improved thermal interface property of carbon nanotube–Cu composite based on supercritical fluid deposition

In this paper, we present a new synthesis method of carbon nanotubes (CNTs)-copper (Cu) composite on a silicon substrate using combination of supercritical fluid deposition (SCFD) and electrochemical plating (ECP) process. Deposition of a Cu layer onto CNTs is carried out under supercritical condition, and the CNTs–Cu composite with high-density Cu is synthesized by additional ECP process. The Cu layer deposited by SCFD functions as a seed layer for ECP, and spaces between neighboring CNTs are filled by Cu. The measured density of the CNTs–Cu composite is 8.2 ± 0.3 g/cm³, and the volume percentage of voids is 3–6%. The evaluated thermal resistance including the thermal interface resistance and bulk resistance of the composite is as low as 28.4 mm² K W⁻¹ at a contact pressure of 0.2 MPa. A CNT brush formed on the composite surface can reduce the thermal resistance to be 68.4 mm² K W⁻¹ at a contact pressure of 0.25 MPa. The CNTs–Cu composite shows the ability applicable to many microelectronics applications as a thermal interface material.     

One second growth of carbon nanotube arrays on a glass substrate by pulsed-current heating

We report the very rapid growth of carbon nanotubes (CNTs) at high temperatures that can be tolerated by glass substrates. Glass substrates with metal microelectrodes and sputtered catalysts are heated by a pulsed current in a chemical vapour deposition gas environment for 0.5–1 s to synthesize CNTs of several micrometres in height without damaging the glass substrate. CNTs with structures from single-walled to multi-walled and morphologies from entangled networks to vertically aligned forests are grown simply by changing the nominal thickness of the catalyst, and such CNTs grown selectively on the microelectrodes worked as field emitters for cathodoluminescence. Rapid, easy growth of patterned CNT arrays on glass substrates without using furnaces/heaters or vacuum pumps will be useful for various applications of CNTs.     

High-performance field emission from a carbon nanotube carpet

We have created a field emitter composed of a carbon nanotube (CNT) yarn, which was prepared by direct spinning through chemical vapor deposition and then formed into a carpet structure by tying the yarn to a conductive substrate before cutting it. The structure of the carpet is arranged to induce the tips of the CNT yarn to protrude toward the anode for maximum electron emission. The turn-on field, threshold field, and field enhancement factor of the device are 0.33, 0.48 V/μm, and 19,141, respectively. Extremely low operating electric fields and a high field enhancement factor result from the high density of CNT emitters with high crystallinity, the electrically good contact between the emitters and the substrate, and the effects of the multistage structure. The emission is stable even at a high current density of 2.13 mA/cm², attributed to the strong adhesion between the emitters and the substrate. The emission performance is found to be customizable by adjusting the structure, for example, the CNT pile density. These results are relevant for practical applications, such as large-area flat-panel displays, large-area low-voltage lamps, and X-ray sources.     

RF-PECVD growth and nitrogen plasma functionalization of CNTs on copper foil for electrochemical applications

This work describes an efficient way to improve the adhesion, growth rate and density of CNTs on copper substrate using radio-frequency plasma enhanced chemical vapor deposition (RF-PECVD). The adhesion of an alumina buffer layer to the copper substrate is critical for the successful growth of CNTs. Hydrogen plasma was performed on the copper substrate to reduce copper oxide from the surface. The effect of two intermediate layers (Ti, Ni), as individual or in combination, between alumina and copper substrate on the CNT growth has been investigated. Furthermore, a nitrogen plasma treatment was carried out to functionalize the obtained CNTs. Electrochemical measurements were performed using CNTs grown on a copper substrate as electrodes and LiClO₄ as electrolyte. The specific capacitance of the obtained electrodes increases from 49 up to 227 Fg^− 1 for untreated and nitrogen-plasma treated CNTs at a scan rate of 10 mVs^− 1, respectively.     

Enhanced field emission properties from titanium-coated carbon nanotubes

The effect of titanium (Ti) coating over the surface of carbon nanotubes (CNTs) on field emission characteristics was investigated. Vertically aligned CNTs were grown by inductively-coupled plasma-enhanced chemical vapor deposition (ICP-CVD). In order to reduce the screening effect of electric field due to densely packed CNTs, as-grown CNTs were partly etched back by DC plasma of N₂. Ti with various thicknesses from 5 nm to 150 nm was coated on CNTs by a sputtering method. Since thick Ti coating with thickness of 100 nm or more resulted in the shape of a metal post by merging an individual CNT in a bundle, it was inadequate to a field emission application. On the other hand, thin Ti-coated CNTs with thickness of 10 nm or less showed a lower turn-on field, a higher emission current density, and improved emission uniformity compared with pristine CNTs. The improved emission performance was mainly attributed to the low work function of Ti and the reliable and lower resistance contact between CNTs and substrates.     

Field emission characteristics of CNFB-CNT hybrid material grown by one-step MPCVD

A hybrid material consisting of carbon nanotubes (CNTs) and carbon nanoflake balls (CNFBs) was successfully synthesized by microwave-plasma-assisted chemical vapor deposition using a H₂/CH₄/N₂ ratio of 4:1:2 at 80 Torr for 30 min. The precursor used was a sol-gel solution containing ferric nitrate, tetrabutyl titanate, and n-propanol. The carbon hybrid material (CNFB-CNT) exhibited excellent field emission properties, with its turn-on field being 1.77 V/μm. It also showed two field enhancement factors (1536 and 7932) for different electric fields. The emission current density of the hybrid remained higher than 0.65 mA/cm² for more than 50 h and was 0.82 mA/cm² even after 50 h of continuous emission. Further, the field emission properties of the CNFB-CNT hybrid were better than those of other single-structured carbon nanomaterials (CNTs, CNFs, or CNFBs). Therefore, the CNFB-CNT hybrid material should be a promising candidate for use in high-performance field emitters.     

Single stage production of carbon nanotubes using microwave technology

Carbon nanotubes (CNTs) were produced by gas phase single stage tubular microwave chemical vapor deposition (TM–CVD) using ferrocene as a catalyst and acetylene (C₂H₂) and hydrogen (H₂) as precursor gasses. The effect of the process parameters such as microwave power, radiation time, and gas ratio of C₂H₂/H₂ was investigated. The CNTs were characterized using scanning and transmission electron microscopy (TEM), and by thermogravimetric analysis (TGA). Results reveal that the optimized conditions for CNT production were 900 W reaction power, 35 min radiation time, and 0.6 gas ratio of C₂H₂/H₂. TEM analyses revealed that the uniformly dispersed vertical alignment of multiwall carbon nanotubes (MWCNTs) have diameters ranging from 16 to 23 nm. The TGA analysis showed that the purity of CNT produced was 98%.     

CVD growth and field electron emission of aligned carbon nanotubes on oxidized Inconel plates without addition of catalyst

Direct growth of carbon nanotubes (CNTs) on Inconel 600 sheets was investigated using plasma enhanced hot filament chemical vapor deposition in a gas mixture of methane and hydrogen. The Inconel 600 sheets were oxidized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) before CNT deposition. The structure and surface morphology of the pre-treated substrate sheets and the deposited CNTs were studied by scanning electron microscopy (SEM) and X-ray diffraction. The field electron emission (FEE) properties of the CNTs were also tested. The SEM results show that well aligned CNTs have been grown on the pre-treated Inconel sheets without addition of any catalysts and the higher treatment temperature resulted in CNTs with better uniformity, indicating that the oxidation pre-treatment of the substrate is effective to enhance the CNT growth. FEE testing shows that CNTs with better height uniformity exhibit better FEE characteristics.     

Field emission properties of as-grown multiwalled carbon nanotube films

Multiwalled carbon nanotubes have been produced by ethylene catalytic chemical vapor deposition and used to fabricate thick and dense freestanding films (“buckypapers”) by membrane filtering. Field emission properties of buckypapers have been locally studied by means of high vacuum atomic force microscopy with a standard metallic cantilever used as anode to collect electrons emitted from the sample. Buckypapers showed an interesting linear dependence in the Fowler–Nordheim plots demonstrating their suitability as emitters. By precisely tuning the tip-sample distance in the submicron region we found out that the field enhancement factor is not affected by distance variations up to 2 μm. Finally, the study of current stability showed that the field emission current with intensity of about 3.3 × 10^?5 A remains remarkably stable (within 5% fluctuations) for several hours.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Fabrication of double-sided field-emission light source using a mixture of carbon nanotubes and phosphor sandwiched between two electrode layers

A double-sided surface light source based on field emission (FE) using an alternating current power source is demonstrated. Carbon-nanotube (CNT) emitters and ZnS phosphor are mixed and screen-printed onto two pieces of indium tin oxide glass that were assembled together with the coated surfaces facing each other to make a parallel-plate, diode-structure FE device. The device has a double-sided luminance distribution with a turn-on field of 2 V/μm, a good uniformity, and a stable luminance of 4000 cd/m². The results show that CNTs not only act as good field emitters but also as an electrically conductive network around the isolated phosphors. The network prevents electric arcing and thus extends the lifetime of the device.     

Effect of substrate heating and microwave attenuation on the catalyst free growth and field emission of carbon nanotubes

Carbon nanotubes (CNTs) have been directly grown on Inconel 600 substrates by microwave plasma enhanced chemical vapor deposition without using any external catalyst. Grown CNTs were characterized by field emission scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy and field emission measurements. Characterization results show that field emission current density increases from 200 μA/cm² at ∼5.5 V/μm to 14.5 mA/cm² at ∼1.6 V/μA when substrate is heat-treated and incident microwave is attenuated before reaching it. Detailed characterization reveals that heat-treatment results in migration of Cr and Fe oxides towards the top surface which completely changes substrate morphology also. Microwave attenuation reduces reflection of microwaves from the substrate and increases residence time of the precursor over the substrate promoting high density growth of CNTs. The combination of these two process parameters resulted in growth of long, dense CNTs with bamboo-like defects that contributes to enhanced current density at lower applied field.