Electron field emission characteristics of different surface morphologies of ZnO nanostructures coated on carbon nanotubes

The optimal carbon nanotube (CNT) bundles with a hexagonal arrangement were synthesized using thermal chemical vapor deposition (TCVD). To enhance the electron field emission characteristics of the pristine CNTs, the zinc oxide (ZnO) nanostructures coated on CNT bundles using another TCVD technique. Transmission electron microscopy (TEM) images showed that the ZnO nanostructures were grown onto the CNT surface uniformly, and the surface morphology of ZnO nanostructures varied with the distance between the CNT bundle and the zinc acetate. The results of field emissions showed that the ZnO nanostructures grown onto the CNTs could improve the electron field emission characteristics. The enhancement of field emission characteristics was attributed to the increase of emission sites formed by the nanostructures of ZnO grown onto the CNT surface, and each ZnO nanostructure could be regarded as an individual field emission site. In addition, ZnO-coated CNT bundles exhibited a good emission uniformity and stable current density. These results demonstrated that ZnO-coated CNTs is a promising field emitter material.     

X-ray images obtained from cold cathodes using carbon nanotubes coated with gallium-doped zinc oxide thin films

X-ray imaging data obtained from cold cathodes using gallium-doped zinc oxide (GZO)-coated CNT emitters are presented. Multi-walled CNTs were directly grown on conical-type (250 μm-diameter) tungsten-tip substrates at 700 °C via inductively coupled plasma-chemical vapor deposition (ICP-CVD). GZO films were deposited on the grown CNTs at room temperature using a pulsed laser deposition (PLD) technique. Field-emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) were used to monitor the variations in the morphology and microstructure of the CNTs before and after GZO coating. The formation of the GZO layers on the CNTs was confirmed using energy-dispersive X-ray spectroscopy (EDX). The CNT-emitter that was coated with a 10-nm-thick GZO film displayed an excellent performance, such as a maximum emission current of 258 μA (at an applied field of 4 V/μm) and a threshold field of 2.20 V/μm (at an emission current of 1.0 μA). The electric-field emission characteristics of the GZO-coated CNT emitter and of the pristine (i.e., non-coated) CNT emitter were compared, and the images from an X-ray system were obtained by using the GZO-coated CNT emitter as the cold cathode for X-ray generation.     

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.     

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.     

Novel low temperature synthesis of ZnO nanostructures and its efficient field emission property

We have developed a novel, simple and cost effective wet chemical synthetic route for the production of ZnO nanoneedles and nanoflowers at low temperature. The synthesis process does not require any surfactant, template or pre-seeding. The synthesized ZnO nanoneedles have very sharp tips with their lengths in the range 2-3 μm, while for the case of nanoflowers, the nanoneedles were bunched together. X-ray diffraction study and X-ray photoelectron spectroscopic studies confirmed the formation of pure ZnO phase. Studies on the electron field emission property of the grown nanostructures showed that they are very efficient field emitter. The turn-on fields and the threshold fields are 3.6 V/μm, 4.4 V/μm and 5.4 V/μm, 6.8 V/μm for the ZnO nanoneedles and ZnO nanoflowers, respectively. The enhanced field emission property was attributed to the presence of sharp tips of the nanostructures.     

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.     

Electrochemical detection of nitrite based on the polythionine/carbon nanotube modified electrode

In this paper, thionine was electro-polymerized onto the surface of carbon nanotube (CNT)-modified glassy carbon (GC) to fabricate the polythionine (PTH)/CNT/GC electrode. It was found that the electro-reduction current of nitrite was enhanced greatly at the PTH/CNT/GC electrode. It may be demonstrated that PTH was used as a mediator for electrocatalytic reduction of nitrite, and CNTs as an excellent nanomaterial can improve the electron transfer between the electrode and nitrite. Therefore, based on the synergic effect of PTH and CNTs, the PTH/CNT/GC electrode was employed to detect nitrite, and the high sensitivity of 5.81 μA mM^− 1, and the detection limit of 1.4 × 10^− 6 M were obtained. Besides, the modified electrode showed an inherent stability, fast response time, and good anti-interference ability. These suggested that the PTH/CNT/GC electrode was favorable and reliable for the detection of nitrite.     

Fabrication and characterization of tetrapod-like ZnO nanostructures prepared by catalyst-free thermal evaporation

Tetrapod-like ZnO nanostructures were fabricated on ZnO-coated sapphire (001) substrates by two steps: pulsed laser deposition (PLD) and catalyst-free thermal evaporation process. First, the ZnO films were pre-deposited on sapphire (001) substrates by PLD. Then the ZnO nanostructures grew on ZnO-coated sapphire (001) substrate by the simple thermal evaporation of the metallic zinc powder at 900 °C in the air without any catalysts. The pre-deposited ZnO films by PLD on the substrates can provide growing sites for the ZnO nanostructures. The as-synthesized ZnO nanostructures were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectrum (FTIR). The results show that the tetrapod-like ZnO nanostructures are highly crystalline with the wurtzite hexagonal structure. Photoluminescence (PL) spectrum of as-synthesized nanostructures exhibits a UV emission peak at ～ 389 nm and a broad green emission peak at ～ 513 nm. In addition, the growth mechanism of ZnO nanostructures is also briefly discussed.     

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.     

Field emission from zinc oxide nanostructures and its degradation

Arrays of zinc oxide (ZnO) nanowires and nanobelts were synthesized by the thermal evaporation of mixed powders of ZnO and graphite. Neither catalyst nor vacuum environment was involved in the fabrication. For comparison, the ZnO nanowires were grown on a pre-deposited transitional ZnO film on a brass substrate and the ZnO nanobelts were grown directly on a Si substrate. Their field emission properties were systematically measured. Current density of 10 μA/cm² was achieved at the fields of 5.7 and 6.2 V/μm from the nanowires and nanobelts, respectively. Also, the emission sites were found to distribute uniformly on the whole cathode. In the preliminary test on the stability, the ZnO nanobelts, which were sharp at the tip but wide at the root, exhibited better robustness than the ZnO nanowires. The post-test scanning electron microscopy (SEM) observation showed that the degradation of their field emission capability resulted from the breaking of the nanowires, which was tentatively attributed to the resistive heating during the field emission. In contrast, the shedding of the ZnO from the substrate was not so serious as imagined.     

Field emission from carbon nanotubes in DC and pulsed mode

Multi-wall Carbon Nanotube (CNT) emitters were tested in a combined diode-RF electron gun. Field emission of the nanotubes was observed at 5-30 MV/m, using a 250 ns FWHM long pulse with a peak voltage of 80-470 kV. The field emission threshold is compatible with that found from previous DC testing. We have extracted from a continuous field emitter up to a nanoCoulomb of charge and measured an emittance of 4 mm mrad with a 2 pC electron beam. The total charge emission during RF operation, using the 1.5 GHz, 2 cell RF structure, was found dependent on its period. RF operation showed that back bombarding electrons with up to 5 MeV did not impair the emission stability of the CNTs.     

Growth and characterization of carbon nanofibers by a technique of polymer doped catalyst and hot-filament chemical vapor deposition

Carbon nanostructures have been prepared from the catalytic conversion of polyethylene glycol using a rapid immersion in hot-filament system fed with ethanol, hydrogen and argon. Fiber structures of external diameter about 30 nm have been observed by field emission scanning electron microscopy (FESEM). Raman measurements indicate high degree of C-C sp² ordering which suggests that the samples correspond to CNTs of good tube crystallinity. The samples presented remarkable field emission properties. Lowest threshold field achieved for electron emission was 1.0 V/μm.     

Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

Rapid synthesis of pure and narrowly distributed Eu doped ZnO nanoparticles by solution combustion method

Pure ZnO:Eu³⁺ nanoparticles (~ 50 nm) were prepared by a solution combustion method. ZnO and Eu₂O₃ were used as starting materials and dissolved in nitric acid. Citric acid was used as a fuel. The reaction mixture was heated at 350 °C resulting into a rapid exothermic reaction yielding pure nanopowders. The atomic weight concentration of Eu³⁺ doped in ZnO was 20%. Transmission electron microscopy (TEM) was used to study the particle size and morphology. The nanopowders were characterized for phase composition using X-ray diffractrometry (XRD). Particle size distribution (PSD) analysis of ZnO: Eu³⁺ showed particle sizes ranging from 30 to 80 nm.The photoluminescence emission spectra of ZnO:Eu³⁺ nanostructures showed a strong band emission around 618 nm when excited with 515 nm wavelength.     

Enhanced and stable electron emission of carbon nanotube emitter arrays by post-growth hydrofluoric acid treatment

Carbon nanotubes (CNT) have been highlighted as possible candidates for field-emission emitters and vacuum nanoelectronic devices. In this article, we studied the effect of acid treatment of CNTs on field emission from carbon nanotube field emitter arrays (FEAs), grown using the resist-assisted patterning process (RAP). The emission current densities of as grown CNT-FEAs and those which were later immersed in hydrofluoric acid (HF) for 20 s, were 19 μA/cm² and 7.0 mA/cm², respectively, when measured at an anode field of 9.2 V/μm. Hence, the emission current densities after HF treatment are 300 times larger than those of as grown CNT-FEAs. Also, it was observed that a very stable electron emission current was obtained after stressing the CNTs with an electric field of 9.2 V/μm for 800 min in dc-mode, where the emission current non-uniformity was 0.13%. The enhancement in electron emission after HF treatment appears to be due to the effect of fluorine bonding. Also, the electron emission characteristics and structural improvement of CNT-FEAs after HF treatment are discussed.     

Influence of VI/II ratios on the growth of ZnO thin films on sapphire substrates by low temperature MOCVD

We investigated the structural, electrical, and optical properties of ZnO thin films grown at different VI/II ratios on sapphire substrates by metalorganic chemical vapor deposition. Transmission electron microscopy and X-ray diffraction revealed the epitaxial nature with a reduced dislocation density of the ZnO films grown at increased VI/II ratios. The carrier concentration of the films increased to 4.9 × 10¹⁸ cm^− 3 and their resistivity decreased to 1.4 × 10^− 1 Ω cm at a VI/II ratio of 513.4 μmol/min. The ZnO films also showed good optical transmittance (> 80%) in the visible and near-infrared wavelength regions. The room temperature PL revealed a strong band-edge emission with a weak deep level emission, suggesting the good crystalline quality of the ZnO films on the sapphire substrates. Furthermore, the intensity ratio of the band-edge emission to the deep-level emission (I_UV/I_Vis) increased with increasing VI/II ratio.     

Magnetic field enhances the graphitized structure and field emission effect of carbon nanotubes

This study uses a low temperature thermal chemical vapor deposition with an applied external magnetic field to grow carbon nanotubes (CNTs) on Ni/Ag-printed glass substrates. A mixture of C₂H₂ and H₂ gas was used for the growth of the CNTs. A Ni catalyst layer was deposited on the Ag-printed glass substrate by pulse electroplating. Scanning electron micrographs as well as the presence of two sharp peaks at 1320 cm⁻¹ (D band) and 1590 cm⁻¹ (G band) in the Raman spectra indicate that the graphitized structure of CNTs synthesized under a magnetic field has higher quality (i.e., a D-band to G-band intensity ratio of 0.303) than CNTs synthesized without a magnetic field. Transmission electron micrographs show a fine Ni catalyst at the tip of the tube for CNTs synthesized under a magnetic field, exhibiting a CNT “tip-growth” model. The synthesis of CNTs in the presence of a magnetic field also generates better field emission properties and better lighting morphology than without a magnetic field.     

Field emission from oriented tin oxide rods

Tin oxide (SnO₂) films were grown on silicon substrates by a wet chemical route. It was found from scanning electron microscopy investigations that oriented SnO₂ rods normal to the substrates were obtained. Field emission studies were carried out in diode configuration in an all metal ultra high vacuum chamber at a base pressure ∼ 1.33 × 10^− 8 mbar. The ‘onset’ field required to draw 0.1 μA/cm² current density from the emitter cathode was found to be ∼ 3.4 V/μm for SnO₂ rods. The field emission current and applied field follows the Folwer-Nordheim relationship in low field regime. The observed results indicate that the field emission characteristics of chemically grown SnO₂ structures are comparable to the vapor grown nanostructures.     

Defect induced room temperature ferromagnetism in well-aligned ZnO nanorods grown on Si (100) substrate

In this work, we report the fabrication of high quality single-crystalline ZnO nanorod arrays which were grown on the silicon (Si) substrate using a microwave assisted solution method. The as grown nanorods were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photo-luminescence (PL) and magnetization measurements. The XRD results indicated that the ZnO nanorods are well oriented with the c-axis perpendicular to the substrate and have single phase nature with the wurtzite structure. FE-SEM results showed that the length and diameter of the well aligned rods is about ~ 1 μm and ~ 100 nm respectively, having aspect ratio of 20-30. Room-temperature PL spectrum of the as-grown ZnO nanorods reveals a near-band-edge (NBE) emission peak and defect induced green light emission. The green light emission band at ~ 583 nm might be attributed to surface oxygen vacancies or defects. Magnetization measurements show that the ZnO nanorods exhibit room temperature ferromagnetism which may result due to the presence of defects in the ZnO nanorods.     

Rapid synthesis of ZnO ellipsoidal nanostructures in large scale and their photoluminescence properties

ZnO ellipsoidal nanostructures with uniform ellipsoidal morphologies have been synthesized using different hydroxide anion precursors by an ultra-fast, facile (90 °C) solution-phase method without the assistance of sonication or any surfactants. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) measurements. Based on the experimental results, a growth mechanism of ZnO nanostructures was proposed. The obtained ZnO nanostructures exhibit a weak UV emission band at ~ 385 nm and a relatively stronger orange emission band at ~ 615 nm. The solution-phase method is simple, convenient for large-scale fabrication of ZnO ellipsoidal nanostructures.