Simple approach for the fabrication of carbon nanotube field emitter using conducting paste

A conducting layer using carbon nanotube (CNT) paste was prepared by mixing multi-walled CNT (MWNT), organic vehicles and spin on glass (SOG). The effect of SOG on the properties of the CNT paste was evaluated and compared to that of CNT paste with a glass frit. CNT powders were coated on the conducting CNT film either by sprinkling CNT powders onto the overall conducting layer area or by dropping a solution containing well dispersed CNTs. CNTs were strongly fixed by the formation of silica after heat treatment. The samples showed good field emission characteristics with turn-on electric fields of approximately 1.6 ∼ 2.2 V/μm. SOG was found to be an efficient inorganic binder for CNTs in the CNT paste.     

Field emission properties of carbon nanotubes synthesized by capillary type atmospheric pressure plasma enhanced chemical vapor deposition at low temperature

Carbon nanotubes (CNTs) were grown using a modified atmospheric pressure plasma with NH₃(210 sccm)/N₂(100 sccm)/C₂H₂(150 sccm)/He(8 slm) at low substrate temperatures (?500 °C) and their physical and electrical characteristics were investigated as the application to field emission devices. The grown CNTs were multi-wall CNTs (at 450 °C, 15-25 layers of carbon sheets, inner diameter: 10-15 nm, outer diameter: 30-50 nm) and the increase of substrate temperature increased the CNT length and decreased the CNT diameter. The length and diameter of the CNTs grown for 8 min at 500 °C were 8 μm and 40 ± 5 nm, respectively. Also, the defects in the grown CNTs were also decreased with increasing the substrate temperature (The ratio of defect to graphite (I_D/I_G) measured by FT-Raman at 500 °C was 0.882). The turn-on electric field of the CNTs grown at 450 °C was 2.6 V/μm and the electric field at 1 mA/cm² was 3.5 V/μm.     

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).     

The use of camphor-grown carbon nanotube array as an efficient field emitter

Three-dimensional growth of well-aligned high-purity multiwall carbon nanotubes (CNTs) is achieved on silicon, nickel-coated silicon and cobalt-coated silicon substrates by thermal decomposition of a botanical carbon source, camphor, with different catalyst concentrations. Field emission study of as-grown nanotubes in a parallel-plate diode configuration suggests them to be an efficient emitter with a turn-on field of ∼1 V/μm (for 10 μA/cm²) and a threshold field of ∼4 V/μm (for 10 mA/cm²). Maximum current density lies in a range of 20-30 mA/cm² at 5.6 V/μm with significant reversibility. Prolonged stability test of camphor-grown CNT emitters suggests a life time of ∼5 months under continuous operation. A new feature, metal-assisted electron emission from CNTs, has been addressed. Isolated nanotubes used as a cold cathode in a field emission microscope reveal the pentagonal emission sites and hence the atomic structure of the nanotube tips.     

Prevention of Si-contaminated nanocone formation during plasma enhanced CVD growth of carbon nanotubes

We investigated the growth behavior and morphology of vertically aligned carbon nanotubes (CNTs) on silicon (Si) substrates by direct current (DC) plasma enhanced chemical vapor deposition (PECVD). We found that plasma etching and precipitation of the Si substrate material significantly modified the morphology and chemistry of the synthesized CNTs, often resulting in the formation of tapered-diameter nanocones containing Si. Either low bias voltage (∼500 V) or deposition of a protective layer (tungsten or titanium film with 10-200 nm thickness) on the Si surface suppressed the unwanted Si etching during growth and enabled us to obtain cylindrical CNTs with minimal Si-related defects. We also demonstrated that a gate electrode, surrounding a CNT in a traditional field emitter structure, could be utilized as a protection layer to allow growth of a CNT with desirable high aspect ratio by preventing the nanocone formation.     

Enhanced electron emission from functionalized carbon nanotubes with a barium strontium oxide coating produced by magnetron sputtering

Carbon nanotubes (CNTs) were functionalized with a surface coating using magnetron sputter deposition. The CNT samples used were prepared by plasma enhanced chemical vapor deposition and were vertically aligned to the surface of the tungsten substrate. A thin layer of barium strontium oxide approximately 100 nm in thickness was deposited on their surface using magnetron sputtering. The oxide coating was uniform, covering the whole surface of the CNTs and significantly lowered the work function while preserving the geometry. The resulting oxide coated CNTs had a work function of 1.9 eV and a field enhancement factor of 467, which led to a significant improvement in both field and thermionic emission. Compared to uncoated CNTs, the field emission was increased by a factor of two, while the thermionic emission increased by more than four orders of magnitude. At 4.4 V/μm, a field emission current of 23.6 μA was obtained from an emitting surface of 0.012 cm². Similarly, at 1.1 V/μm and 1221 K, a thermionic emission current of 14.6 mA was obtained.     

Synthesis of well-aligned carbon nanotubes with open tips

Large amounts of well-aligned carbon nanotubes (CNTs) with open tips have been produced by pyrolysis of iron(II) phthalocyanine. The aligned CNTs have an average length about 10 μm and diameters ranging from 92 to 229 nm. Some of produced CNTs showed Y-junction structure due to the self-joint growth of two neighboring CNTs. The well-aligned CNTs indicated a bamboo-shaped multiwalled structure and fairly good crystallinity. The aligned CNTs follow tip growth mechanism.     

The effect of atmospheric pressure plasma treatment on the field emission characteristics of screen printed carbon nanotubes

The effects of pin-to-plate type atmospheric pressure plasma treatment on the field emission properties of screen printed carbon nanotubes(CNTs) were investigated using He(10 slm)/N₂(0.1 slm). The plasma treatment for 10 s decreased the turn-on field from 3.13 V/μm to 1.21 V/μm, increased the emission current, and increased the number of emission sites. When, the 10 s plasma treatment was also applied to the CNTs which were previously treated by a tape activation method, the number of emission sites were further increased, therefore, the emission uniformity was improved even though, the plasma treatment on the tape-activated CNTs increased the turn-on field slightly 0.76 V/μm to 1.25 V/μm due to the removal of long CNTs.     

Growth and electrical characterization of high-aspect-ratio carbon nanotube arrays

The remarkable properties of carbon nanotubes (CNTs) make them attractive for microelectronic applications, especially for interconnects and nanoscale devices. In this paper, we describe a microelectronics compatible process for growing high-aspect-ratio CNT arrays with application to vertical electrical interconnects. A lift-off process was used to pattern catalyst (Al₂O₃/Fe) islands to diameters of 13 or 20 μm. After patterning, chemical vapor deposition (CVD) was involved to deposit highly aligned CNT arrays using ethylene as the carbon source, and argon and hydrogen as carrier gases. The as-grow CNTs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CNTs have high purity, and form densely-aligned arrays with controllable array size and height. Two-probe electrical measurements of the CNT arrays indicate a resistivity of ∼0.01 Ω cm, suggesting possible use of these CNTs as interconnect materials.     

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.     

The effect of feedstock and process conditions on the synthesis of high purity CNTs from aromatic hydrocarbons

High purity multi-walled carbon nanotubes were synthesized from aromatic hydrocarbons (benzene, toluene, xylene and trimethyl benzene) using ferrocene as the source of Fe catalyst. Screening studies of aromatic feeds at 675 °C, residence time of 14 s and Fe/C atom ratio of 1.07%, resulted in feedstock carbon conversion of 20-31%, CNT yield of 19.8-30.5%, and catalyst yield of 5.3-8.3 (g CNT/g catalyst). While the quality of the CNTs as determined by TGA, SEM, TEM and Raman spectroscopy, were high and comparable for different feedstocks; their carbon conversion, CNT yield and catalyst yield differed noticeably. A process optimization study for toluene feed showed that carbon conversion of more than 39%, CNT yield of 38.7% and catalyst yield of 18.3 can be achieved at temperature of 800 °C, Fe/C atom ratio of 0.47%, and residence time of 10-20 s.     

Local field emission from individual vertical carbon nanofibers grown on tungsten filament

Individual high-aspect-ratio carbon nanofibers (CNFs) were grown on tungsten filament substrates by plasma-enhanced hot filament chemical vapor deposition. They are ∼100 nm in diameter and 6-30 μm in length with a density less than 10⁶/cm². The field emission property of single as-grown carbon nanofibers was measured in a scanning electron microscope equipped with a moveable nanoscale probe tip. The measurement results showed that the threshold field of single carbon nanofibers with different lengths was in the range of 4-5 V/μm with a corresponding emission current density of 20 μA/cm², but an evident difference in the enhancement of emitted current between nanofibers of different lengths could be found when the applied field was increased continuously. This indicates that the field emission property of single carbon nanofibers depends mainly upon their length, which is essentially attributed to the change of field enhancement factor of single carbon nanofibers. In addition, field emission of the different positions on the wall of a single carbon nanofiber was studied.     

Vertically aligned carbon nanotube arrays grown on a lamellar catalyst by fluidized bed catalytic chemical vapor deposition

Large amount of vertically aligned carbon nanotube (CNT) arrays were grown among the layers of vermiculite in a fluidized bed reactor. The vermiculite, which was 100-300 μm in diameter and merely 50-100 μm thick, served as catalyst carrier. The Fe/Mo active phase was randomly distributed among the layers of vermiculite. The catalyst shows good fluidization characteristics, and can easily be fluidized in the reactor within a large range of gas velocities. When ethylene is used as carbon source, CNT arrays with a relatively uniform length and CNT diameter can be synthesized. The CNTs in the arrays are with an inner diameter of 3-6 nm, an outer diameter of 7-12 nm, and a length of up to several tens of micrometers. The as-grown CNTs possess good alignment and exhibit a purity of ca. 84%. Unlike CNT arrays grown on a plane or spherical substrate, the CNT arrays grown in the fluidized bed remain their particle morphologies with a size of 50-300 μm and the good fluidization characteristics were preserved accordingly.     

Catalytic synthesis of carbon nanotubes using Ni- and Co-doped calcium tartrates

Calcium tartrate doped with Ni and/or Co has been used as a catalyst source in the chemical vapor deposition synthesis of carbon nanotubes (CNTs). Thermolysis of doped calcium tartrate in an inert atmosphere was shown to yield Ni, Co or Ni-Co nanoparticles ∼6 nm in diameter dispersed in a calcium oxide matrix. The CNT synthesis was carried out by ethanol vapor decomposition at 800 °C. The structure of the products was characterized by transmission electron microscopy and Raman spectroscopy. It was found that Ni nanoparticles embedded in CaO provide the narrowest diameter distribution of CNTs, while the bimetallic Ni-Co catalyst allows the formation of the thinnest CNTs with the outer diameter of ∼2 nm. This type of CNT is more likely to be responsible for the lowest value of the turn-on field (∼1.8 V/μm) for the emission current detected for the latter sample.     

Influence of catalytic particle size on the performance of fluidized-bed chemical vapor deposition synthesis of carbon nanotubes

In this paper, the impacts of catalytic particle size on the overall reactor performance for carbon nanotubes (CNTs) production using a fluidized-bed chemical vapor deposition (FBCVD) process have been studied. Six different particle size fractions (10-20 μm, 20-53 μm, 53-75 μm, 75-100 μm, 100-200 μm, and 200-300 μm) were selected. It was observed that the smaller the catalytic particle diameter, the greater the carbon deposition efficiency and the greater CNT synthesis selectivity. The 10-20 μm catalytic particles exhibited 30% higher carbon deposition efficiency than the 200-300 μm catalytic particles. The selectivity toward CNTs formation was also approximately 100%. These observations could be explained by the fact that when the diameter of the catalytic particle gets smaller, the breakthrough capacities during frontal diffusion will be bigger due to a shorter diffusion path length within the particle. Moreover, the fine particles ensured high interstitial velocity which subsequently enhances the heat and mass transfer, and consequently improves the CVD reaction.     

Synthesis of nitrogen-doped horn-shaped carbon nanotubes by reduction of pentachloropyridine with metallic sodium

Nitrogen-doped horn-shaped carbon nanotubes (CNTs) have successfully been prepared by reducing pentachloropyridine with metallic sodium at 350 °C. A typical CNT has an open-end diameter of ∼2 μm, a close-end diameter of ∼0.3 μm, a wall thickness of ∼30 nm, and a length up to 8 μm. TEM observation indicates that the CNTs account for ∼30% of the products, and the rest is solid and hollow carbon nanospheres (CNSs) with a diameter of about 50-290 nm. Elemental analysis shows that the N/C atomic ratio of the carbon nanostructures is about 0.0208. XRD and HRTEM measurements reveal that the CNTs are amorphous. To understand the growth process and refine the growth condition, various control experiments have been finished. At last, a sodium-catalysis-reduction solid-liquid-solid growth mechanism of the CNTs has been suggested on the basis of the experiments.     

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.     

Easy synthesis of a nanostructured hybrid array consisting of gold nanoparticles and carbon nanotubes

A nanostructured hybrid consisting of a high-density and uniform assembly of gold nanoparticles (AuNPs) on carbon nanotubes (CNTs) was prepared using easy methods. The pyrolysis of iron(II) phthalocyanine (FePc) on a Si substrate under an atmosphere of hydrogen/argon was used to produce multiwalled carbon nanotubes (MWCNTs) with 12 nm in diameter and 4 μm in length. Then, Au nanocolloid solution, which contained dodecanethiol-capped Au nanoparticles synthesized by solution chemical method, was deposited on the synthesized CNT array and heated at 300 °C for 1 h under Ar. The synthesis temperature of CNT governs the AuNP-CNT hybrid structure and surface nitrogen concentration from decomposition of FePC. CNTs synthesized at 800 °C exhibit the finest particle size and most homogeneous dispersity of assembled AuNPs in comparison to hybrids whose CNTs are synthesized at other temperatures. These features are considered to correlate with the surface nature of the grown CNT; good dispersity of AuNPs on CNT results from interaction between the thiolate molecules capped on the AuNPs and the N atoms doped into the grown CNT. Assembling AuNPs to CNT contributes the electrical conductivity enhancement of the CNT hybrid array.     

Growth and field emission study of a monolithic carbon nanotube/diamond composite

Carbon nanotube (CNT)/diamond composite has been fabricated by hot filament chemical vapor deposition on a silicon substrate using iron as catalyst. The material characteristics of this monolithic structure were examined by electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The composite material shows the presence of carbon nanotubes of several microns in length together with conspicuous diamond microcrystals of sizes ranging from 0.5 to 2.0 μm. The CNTs protrude from the diamond microcrystals and become entangled around them as they grow. This monolithic CNT/diamond composite provides an intrinsic heat dissipation mechanism for CNTs during field emission and exhibits low turn on field, large field enhancement factor, and an excellent current stability over a period of 44 h.