Controlled growth of carbon nanotube-graphene hybrid materials for flexible and transparent conductors and electron field emitters

We report a versatile synthetic process based on rapid heating and cooling chemical vapor deposition for the growth of carbon nanotube (CNT)-graphene hybrid materials where the thickness of graphene and density of CNTs are properly controlled. Graphene films are demonstrated as an efficient barrier layer for preventing poisoning of iron nanoparticles, which catalyze the growth of CNTs on copper substrates. Based on this method, the opto-electronic and field emission properties of graphene integrated with CNTs can be remarkably tailored. A graphene film exhibits a sheet resistance of 2.15 kΩ sq(-1) with a transmittance of 85.6% (at 550 nm), while a CNT-graphene hybrid film shows an improved sheet resistance of 420 Ω sq(-1) with an optical transmittance of 72.9%. Moreover, CNT-graphene films are demonstrated as effective electron field emitters with low turn-on and threshold electric fields of 2.9 and 3.3 V μm(-1), respectively. The development of CNT-graphene films with a wide range of tunable properties presented in this study shows promising applications in flexible opto-electronic, energy, and sensor devices.     

Field emission properties from aligned carbon nanotube films with tetrahedral amorphous carbon coatings

Tetrahedral amorphous carbon (ta-C) film was coated on aligned carbon nanotube (CNT) films via filtered cathodic vacuum arc (FCVA) technique. Field electron emission properties of the CNT films and the ta-C/CNT films were measured in an ultra high vacuum system. The I–V measurements show that, with a thin ta-C film coating, the threshold electric field (E_thr) of CNTs can be significantly decreased from 5.74 V/μm to 2.94 V/μm, while thick ta-C film coating increased the E_thr of CNTs to around 8.20 V/μm. In addition, the field emission current density of CNT films reached 14.9 mA/cm² at 6 V/μm, while for CNTs film coated with thin ta-C film only 3.1 V/μm of applied electric field is required to reach equal amount of current density. It is suggested that different field emission mechanisms should be responsible for the distinction in field emission features of CNT films with different thickness of ta-C coating.     

Horizontally aligned carbon nanotube field emitters having a long term stability

Horizontally aligned carbon nanotube (CNT) field emitters fabricated by electrophoresis deposition and fissure formation techniques show good field emission properties such as high current density, low turn-on voltage and long-term stability. Horizontally aligned multi-walled carbon nanotube (MWCNT) field emitters show an unusual very long-term stability, much better stability than the single-walled carbon nanotube (SWCNT) ones. The cause of the degradation is due to the heat generated by the resistance of CNTs. We were able to prevent effectively the degradation of the horizontally aligned field emitters by using MWCNTs and an additional deposition of aluminum on the CNT films, and the required time for 10% degradation is very long, 121 h.     

Improvement of electron field emission from carbon nanotubes by Ar neutral beam treatment

To improve the field emission properties of screen printed carbon nanotube (CNT) films, an Ar neutral beam was used as one of the surface treatment techniques and the CNT field emission characteristics after the treatment were compared with those after Ar ion beam treatment. The Ar neutral beam treatment enhanced the field emission properties of the CNTs and by decreasing the turn-on field and by increasing emission sites. When the field emission properties were measured after the treatment for 10 s with an energy of 100 eV, the turn-on field decreased from 1.7 to 0.9 V/μm while that after the ion beam treatment increased from 1.7 to 2.8 V/μm showing damage of exposed CNTs due to the intensive bombardment by the positive ions in the beam. The neutral beam treatment appeared to expose more CNT field emitters from the CNT paste without cutting or severely damaging the already exposed long CNT emitters because there were no charged particles in the beam.     

Horizontally aligned carbon nanotube field emitters fabricated on ITO glass substrates

Horizontally aligned carbon nanotube (CNT) field emitters, in which electrons are emitted from the side of CNTs, are fabricated on indium tin oxide (ITO) glass substrates by electrophoretic deposition and fissure formation techniques. A thin film of CNTs is deposited onto an ITO glass plate using an aqueous mixture of CNTs and the cationic detergent cetyltrimethylammonium bromide by applying a negative voltage to the ITO glass plate. Then, an additional layer of sodium dodecyl sulfate (SDS), an anionic detergent, is deposited on the CNT film. This is done using an aqueous solution of SDS by applying a positive voltage. Through the process of firing, CNTs with a clean surface are exposed in the fissures produced. No further treatment is needed to initiate or augment field emission. The CNT field emitters show relatively good field-emission properties such as high current density (11 mA/cm² at an applied electric field of 4.3 V/μm), low turn-on field (2.2 V/μm), and good stability (98 h for 10% degradation of current density from 400 μA/cm²).     

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.     

Effects of CF4 plasma on the field emission properties of aligned multi-wall carbon nanotube films

We present a simple method to functionalize the surface and to modify the structures of aligned multi-wall carbon nanotube (CNT) arrays grown on silicon substrates using CF₄ plasma produced by reactive ion etching (RIE). Field emission (FE) measurements showed that after 2 min of plasma treatment, the emission currents were enhanced compared with as-grown CNTs; however, extended treatment over 2 min was found to degrade the FE properties of the film. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy have been employed to investigate the mechanism behind the modified FE properties of the CNT film. The FE enhancement after 2 min of etching could be attributed to favorable surface morphologies, open-ended structures and a large number of defects in the aligned CNT films. On the other hand, deposition of an amorphous layer comprising carbon and fluorine during extended CF₄ plasma treatment may hamper the field emission of CNT films.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Stable Field Emitters for a Miniature X-ray Tube Using Carbon Nanotube Drop Drying on a Flat Metal Tip

Stable carbon nanotube (CNT) field emitters for a vacuum-sealed miniature X-ray tube have been fabricated. The field emitters with a uniform CNT coating are prepared by a simple drop drying of a CNT mixture solution that is composed of chemically modified multi-walled CNTs, silver nanoparticles, and isopropyl alcohol on flat tungsten tips. A highly thermal- and electrical-conductive silver layer strongly attaches CNTs to the tungsten tips. Consequently, the field emitters exhibit good electron emission stability: continuous electron emission of around 100 μA at 2.3 V/μm has stably lasted over 40 h even at non-high vacuum ambient (~10⁻³ Pa).     

Bending actuation and charge distribution behavior of polyurethane/carbon nanotube electroactive nanocomposites

The electroactive nanocomposite films were fabricated using polyurethane (PU) with modified carbon nanotubes (CNTs) as the filler. The CNTs were modified using microwave‐induced polymerization route and they were found to be highly dispersed in polar solvents such as dimethylformamide. The modified CNTs were characterized using transmission electron microscopy, field emission scanning electron microscopy, thermogravimetric analysis, and X‐ray photoelectron spectroscopy. To evaluate these films we mainly focused on electrical properties such as actuation behavior, resistivity, impedance analysis, and space charge measurements. We found that the PU/CNT films bent toward the cathode when an electric field was applied and they reverted to its original position when the electric field was removed. Upon the incorporation of CNTs as the filler for the polymer, the electrical properties of the films improved significantly. Asymmetric charge accumulation was observed from space charge measurements in some of the films and this explains the bending deformation and the actuation behavior. POLYM. COMPOS., 262–269, 2016. © 2014 Society of Plastics Engineers     

Highly stable carbon nanotube field emitters on small metal tips against electrical arcing

Carbon nanotube (CNT) field emitters that exhibit extremely high stability against high-voltage arcing have been demonstrated. The CNT emitters were fabricated on a sharp copper tip substrate that produces a high electric field. A metal mixture composed of silver, copper, and indium micro- and nanoparticles was used as a binder to attach CNTs to the substrate. Due to the strong adhesion of the metal mixture, CNTs were not detached from the substrate even after many intense arcing events. Through electrical conditioning of the as-prepared CNT emitters, vertically standing CNTs with almost the same heights were formed on the substrate surface and most of loosely bound impurities were removed from the substrate. Consequently, no arcing was observed during the normal operation of the CNT emitters and the emission current remained constant even after intentionally inducing arcing at current densities up to 70 mA/cm².     

Stretchable conductive films based on carbon nanomaterials prepared by spray coating

Stretchable conductive films consisting of a layer of carbon nanomaterials, that is, carbon nanotubes (CNTs), mechanically exfoliated graphene (GE), or chemically reduced graphene oxide (rGO), deposited on polydimethylsiloxane (PDMS) films were prepared by spray coating. The correlations among the concentration of the carbon nanomaterials, the electrical resistance and the optical transmittance of the spray‐coated films were investigated. The results show that the conductivity of the CNT coatings was better than that of the GE‐based coatings. When the CNT concentration of the dispersion for spraying increased from 0.01 to 0.075 mg/mL, the surface electrical resistance decreased from 7.8 × 10³ to 6.7 × 10² Ω, whereas for the GE or rGO coatings, the electrical resistance was several orders higher than that of the CNT coatings. The CNT spray‐coated films exhibited an optical transmittance of about 60% at a wavelength of 550 nm; this was higher than that of the GE or rGO spray‐coated films. The electric heating behaviors of the stretchable conductive films as functions of the applied voltage and the concentration of carbon nanomaterials and the electrical conductivity under tensile and bending strains were also investigated. The surface temperature of the CNT‐coated films rose rapidly up to 200°C within about 40 s when the applied voltage was 110 V. The stretchable conductive films have potential as electric heating elements because of their excellent conductive properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43243.     

Effect of Substrate Morphology on Growth and Field Emission Properties of Carbon Nanotube Films

Carbon nanotube (CNT) films were grown by microwave plasma-enhanced chemical vapor deposition process on four types of Si substrates: (i) mirror polished, (ii) catalyst patterned, (iii) mechanically polished having pits of varying size and shape, and (iv) electrochemically etched. Iron thin film was used as catalytic material and acetylene and ammonia as the precursors. Morphological and structural characteristics of the films were investigated by scanning and transmission electron microscopes, respectively. CNT films of different morphology such as vertically aligned, randomly oriented flowers, or honey-comb like, depending on the morphology of the Si substrates, were obtained. CNTs had sharp tip and bamboo-like internal structure irrespective of growth morphology of the films. Comparative field emission measurements showed that patterned CNT films and that with randomly oriented morphology had superior emission characteristics with threshold field as low as ~2.0 V/μm. The defective (bamboo-structure) structures of CNTs have been suggested for the enhanced emission performance of randomly oriented nanotube samples.     

Fabrication of Ni-matrix carbon nanotube field emitters using composite electroplating and micromachining

Ni-matrix carbon nanotube (CNT) field emitters have been fabricated by composite electroplating and micromachining (CEMM) at room temperature. Pretreated multi-walled CNT and Ni are deposited onto a Cr/Cu conducting layer by composite electroplating and protruding tips of CNTs are obtained as emitters by etching away a layer of Ni, followed by emitter pixels which are formed by micromachining. Through the process of CEMM, CNTs are vertically embedded in the flat Ni substrate. No further treatment is needed to initiate or augment field emission and the field emitters exhibit good field-emission properties such as high current density (13 mA cm⁻² at an applied electric field of 3.4 V μm⁻¹), low turn-on field (0.53 V μm⁻¹), and good stability (110 h for 10% degradation of current density from 400 μA cm⁻²).     

Optimization of plasma-enhanced chemical vapor deposition parameters for the growth of individual vertical carbon nanotubes as field emitters

In this article plasma enhanced growth of single vertical carbon nanotubes (CNTs) from individual nickel catalyst dots is studied, aiming at the fabrication of CNT field emitters. It is found that the growth of individual CNTs differs from that of CNT forests grown from unpatterned catalyst films, an effect that can be attributed to the difference in catalyst volumes. In the context of growth parameters the influence of temperature, growth time, catalyst volume, pressure and power is characterized. After determining the growth behavior, an individual CNT of desired geometry is fabricated on a conducting lead. The CNT is electrically characterized in terms of its field emission behavior and stable emission currents and its work function is determined to Φ = 5.4 ± 0.2 eV.     

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.     

Array geometry, size and spacing effects on field emission characteristics of aligned carbon nanotubes

Microwave plasma-enhanced chemical vapor deposition (MPECVD) has been shown capable of producing vertically aligned mutli-walled CNTs as a result of self-bias of the microwave plasma. These CNTs are relevant to field emission applications. However, it is also known that closely packed or mat-like CNTs are not effective field emitters due to field screening effects among neighboring tubes. In this study, an approach whereby “micro-” patterning of CNT arrays, adjusting their geometry, size and array spacing by conventional photolithography, rather than “nano-” patterning a single CNT by electron-beam lithography, is employed to fabricate efficient emitters with enhanced field emission characteristics. MPECVD with catalysts are used on Si substrate to fabricate micropatterned vertically aligned CNT arrays with various geometries, sizes and spacing. The field emission results show that a circular array with 20 μm spacing has the lowest turn-on field of 2 V/μm at 1 μA/cm² and achieves the highest current density of 100 μA/cm² at 3 V/μm. Investigation on the array spacing effect shows that 10 × 10 μm CNT square array with an array spacing of 20 μm displays the lowest turn-on field of 9 V/μm and achieved a very high current density of 100 mA/cm² at 20 V/μm. Furthermore, the results suggest that the array spacing of the 10 × 10 μm CNT square array can be reduced to at least 20 μm without affecting the field enhancement factor of the emitter. The results clearly indicate further optimization of spacing in the arrays of CNT emitters could result in lower turn-on field and higher current density.     

Field emission of ribonucleic acid–carbon nanotube films prepared by electrophoretic deposition

Carbon nanotube (CNT) films are fabricated on indium tin oxide (ITO) glass substrates by combining electrophoresis with photolithography using ribonucleic acid (RNA)–CNT hybrids as functionalized CNTs and their emission properties are investigated. The CNTs are well-dispersed by wrapping them with RNA and well-defined RNA–CNT patterns are obtained on the ITO glass substrate. The RNA–CNT films show good field emission properties, such as high current densities, low turn-on fields, and uniform emission images. The RNA–CNT hybrids compare favorably to other functionalized CNTs for use in the electrophoretic deposition.     

Carbon nanotubes field emission devices grown by thermal CVD with palladium as catalysts

The effects of palladium (Pd) catalyst film thickness and ammonia (NH₃) in thermal chemical vapor deposition (CVD) growth of carbon nanotubes (CNTs) are systematically compared per the resulting morphologies, Raman spectra and field emission characteristics. The CNT field emitters were tested under identical experimental configurations. Field emission characteristics were described with Fowler-Nordheim field emission theory. Experimental results demonstrate that thermally grown CVD CNTs configured as diode field emitters exhibit low turn-on fields and high emission current density. The work is extended to include the study of gated field emitters or field emission triode, important to achieving high-resolution, full gray-scale imaging for field emission, flat-panel displays. The gated device was fabricated utilizing single-mask, self-aligned gate electrode with conventional integrated-circuit (IC) fabrication process. The CNT-triode showed gate-controlled modulation of emission current where higher gate voltage gives rise to higher anode currents. The triode fabrication process using silicon-on-insulator (SOI) wafers is discussed.     

Epoxy composites with carbon nanotubes and graphene nanoplatelets – Dispersion and synergy effects

Carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) at different mix ratios were dispersed by ultrasonication into an epoxy matrix and the effects of CNT:GNP ratios on the mechanical and electrical properties of the hybrid composites were investigated. The combination of CNT and GNP in a ratio 8:2 was observed to synergistically increase flexural properties and to reduce the electrical percolation threshold for the epoxy composites, indicating easier formation of a conductive network due to the improved state of CNT dispersion in the presence of GNPs. The state of dispersion was evaluated at different length scales by using optical microscopy, UV–Vis spectroscopy, rheological measurements, scanning electron microscopy, transmission electron microscopy and sedimentation tests. The Fourier transform infrared spectra for CNT and GNP indicate that the GNPs contain oxygen moieties responsible for better interactions with the epoxy matrix.