Enhancing electron field emission of carbon nanoflakes by hydrogen post-annealing process

In this study, the carbon nanoflakes (CNFs) fabricated by sputtering were chosen as the field emission emitters because of their very sharp and thin edges which are potentially good electron field emission sites. The as-deposited CNFs were annealed in the furnace under hydrogen atmosphere. The results showed that the optimum field emission properties with smaller turn-on field and larger current density were obtained at annealing temperature of 600 °C for 10 min. The hydrogen thermal annealing has chemical etching on the surface of the CNFs and produces appropriate emission site density to increase the emission current density. The turn-on field was reduced from 6.7 to 5.8 V/μm and electric current density was increased from 22 to 187 μA/cm² under 8 V/μm after hydrogen thermal annealing.     

Selective growth of well-aligned carbon nanotubes by APCVD

Well-aligned good-quality carbon nanotube (CNT) array was grown on silicon substrate by atmospheric pressure chemical vapor deposition (APCVD) through SiO₂ masking. First, the patterned substrate was pretreated with NH₃ and then CNTs were synthesized at 800 °C using Ni as the catalyst, acetylene (C₂H₂) as the carbon source material and N₂ as the carrier gas. Effects of the NH₃-pretreatment time, the flow ratio of [C₂H₂]/[NH₃] and the CNT growth time on the qualities of CNT array were analyzed in detail. It was found that good-quality CNTs with an average length of around 15 μm could be grown by pretreating the Si substrate with NH₃ for 10 min and then conducting the CNT growth with a flow ratio of [C₂H₂]/[NH₃] = 30/100. Furthermore, the field emission property of CNT array was investigated using a diode structure. It was found that the turn-on electric field decreased with increasing CNT length. The turn-on electric field as low as about 2 V/μm with an emission current density of 10 μA/cm² was achieved for a CNT-array diode with the tube length near 18 μm. For the same device, the emission current density could be elevated to 10 mA/cm² with the applied voltage of 3.26 V/μm.     

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.     

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 characteristics of CNTs synthesized by bias-assisted ICPHFCVD and ICPCVD techniques

Carbon nanotubes (CNTs) were vertically well-grown on Ni/Cr-deposited glass substrates at 580 °C by ICPCVD and bias-assisted ICPHFCVD techniques. The vertically well-aligned CNTs showed multi-walled type with hollow structure. The measured critical current density on CNTs grown by the ICPCVD technique was 1.0×10^–6 A cm^–2 at 5 V m^–1 of turn-on field and 7.7×10^–5 A cm^–2 at 7.8 V m^–1 of the critical field. On the other hand, the critical current density on CNTs grown by the bias-assisted ICPHFCVD technique was 3.7×10^–7 A cm^–2 at 3 V m of turn-on field and 3.3×10^–4 A cm^–2 at 6.8 V m^–1 of the critical field, respectively. On comparing the two processes, it can be concluded that CNTs grown by bias-assisted ICPHFCVD are more suitable than those grown by ICPCVD for the possible application of field emission displays (FEDs).     

Electron field emission properties of carbon nanoflakes prepared by RF sputtering

Carbon nanoflakes (CNFs) with corrugated geometry were synthesized using RF sputtering process with Ar/CH₄ gas mixture. Transmission electron microscopic examination reveals that the introduction of H₂ in sputtering chamber leads to the preferential etching of amorphous carbons, while maintaining integrity for the nano-crystalline phases. The proportion of nano-sized crystalline clusters is thus increased, which improved the electron field emission (EFE) properties of the materials, viz. with turn-on field of E ₀ = 6.22 V/μm and FEE current density of J _e = 90.1 μA/cm² at 11.0 V/μm. The cathodes made of screen printing of CNFs-Ag paste exhibit even better EFE properties than the as-deposited CNFs. The EFE of the CNFs cathodes can be turned on at E ₀ = 5.71 V/μm, achieving J ₀ = 340.1 μA/cm² at 11.0 V/μm applied field. These results showed that the CNFs are inheritantly more robust in device fabrication process than the other carbon materials and thus possess better potential for electron field emitter applications.     

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.     

The emission effect of metal-tip removal in carbon nanotubes by bias-assisted ICPHFCVD

This paper presents a technique for the preparation of vertically grown carbon nanotubes (CNTs) by bias-assisted inductively coupled plasma hot-filament chemical vapor deposition. Purification of the CNTs using r.f. plasma in a one-step process, based on the different etching property of the metal tip is also discussed. The Ni at the tip of the CNTs was effectively removed by using r.f. plasma based on the different etching property. After purification CNTs show the multi-walled and hollow-type structure. The measured critical current density on CNTs with a Ni tip was 3.52×10^–7 A cm^–2 at 2.47 V m^–1 turn-on field and 6.6×10^–4 A cm^–2 at 4.8 V m^–1 of the critical field. On the other hand, the critical current density on purified CNTs after Ni removal by an r.f. source was 1.36×10^–7 A cm^–2 at 2.1 V m^–1 turn-on field and 1.5×10^–3 A cm^–2 at 6 V m^–1 of the critical field, respectively.     

Preparation and field emission properties of titanium polysulfide nanobelt films

TiS₃ nanobelt films, with widths of about 0.1–12 μm, thickness of about 20–250 nm, and lengths of up to 200 μm, have been grown on Ti substrates by a surface-assisted chemical-vapor-transport at 450 °C for 8 h. The TiS₃ nanobelt films were converted into TiS_1.71 nanobelt films by pyrolysis in a vacuum at 600 °C for 2 h. The work functions of the two films were determined by ultraviolet photoelectron spectroscopy measurements to be 4.60 and 4.44 eV, respectively. Preliminary field emission experiments using the nanostructures as cold electron cathodes showed that both materials gave significant emission currents. The turn-on fields (defined as the electric field required to produce a current density of 10 μA/cm₂) were about 1.0 and 0.9 V/μm, respectively, whereas the threshold fields (defined as the electric field required to produce a current density of 1 mA/cm₂) were about 5.6 and 4.0 V/μm, respectively. These data reveal that both materials have potential applications in field emission devices. This article is published with open access at Springerlink.com     

Field emission from the structure of well-aligned TiO2/Ti nanotube arrays

Well-aligned TiO₂/Ti nanotube arrays were synthesized by anodic oxidation of titanium foil in 0.5 wt.% HF in various anodization voltages. The images of filed emission scanning electron microscopy indicate that the nanotubes structure parameters, such as diameter, wall thickness and density, can be controlled by adjusting the anodization voltage. The peaks at 25.3° and 48.0° of X-ray diffraction pattern illuminate that the TiO₂ nanotube arrays annealed at 500 °C are mainly in anatase phase. The filed emission (FE) properties of the samples were investigated. A turn-on electric field 7.8 V/µm, a field enhancement factors approximately 870 and a highest FE current density 3.4 mA/cm² were obtained. The emission current (2.3 mA/cm² at 18.8 V/µm) was quite stable within 480 min. The results show that the FE properties of TiO₂/Ti have much relation to the structure parameters.     

Ultra-thin double-walled carbon nanotubes: A novel nanocontainer for preparing atomic wires

Double-walled carbon nanotubes (DWCNTs) with high graphitization have been synthesized by hydrogen arc discharge. The obtained DWCNTs have a narrow distribution of diameters of both the inner and outer tubes, and more than half of the DWCNTs have inner diameters in the range 0.6–1.0 nm. Field electron emission from a DWCNT cathode to an anode has been measured, and the emission current density of DWCNTs reached 1 A/cm² at an applied field of about 4.3 V/μm. After high-temperature treatment of DWCNTs, long linear carbon chains (C-chains) can be grown inside the ultra-thin DWCNTs to form a novel C-chain@DWCNT nanostructure, showing that these ultra-thin DWCNTs are an appropriate nanocontainer for preparing truly one-dimensional nanostructures with one-atom-diameter.      

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.     

Growth and optical and field emission properties of flower-like ZnO nanostructures with hexagonal crown

Flower-like zinc oxide (ZnO) nanostructures with hexagonal crown were synthesized on a Si substrate by direct thermal evaporation of zinc power at a low temperature of 600 °C and atmospheric pressure. Field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy and photoluminescence were applied to study the structural characteristics and optical properties of the product. The result indicated that the flower-like product with many slender branches and hexagonal crowns at the ends were single-crystalline wurtzite structures and were preferentially oriented in the <001> direction. The photoluminescence spectrum demonstrated a strong UV emission band at about 386 nm and a green emission band at 516 nm. The field emission of the product showed a turn-on field of 3.0 V/µm at a current density of 0.1 μA/cm², while the emission current density reached about 1 mA/cm² at an applied field of 5.9 V/μm.     

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.     

Effective electron emitters by molybdenum oxide-coated carbon nanotubes core–shell nanostructures

In this article, we showed that simple metal oxide coatings such as MoO₃ can be an effective enhancer for carbon nanotubes (CNTs) in field emission (FE) performance. For comparison, the FE properties of the pristine vertically aligned multi-walled CNTs with the metal oxide-coated CNTs were investigated. The metal oxide coating of the pristine CNTs was carried out by metal–organic chemical vapor deposition (MOCVD) method at 400 °C using Mo(CO)₆ as the precursor. The core–shell structure of the nanocomposite was studied by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) results showed that the surface of the coating material was mainly MoO₃. FE test indicated that the MoO₃-coated CNTs film exhibited an enhanced performance than the pristine CNTs with a turn-on field of 1.33 V μm⁻¹ and a field enhancement factor β estimated to be ~7000. Ultraviolet photoelectron spectroscopy (UPS) results confirmed a lower electron emission barrier height for MoO₃-coated CNTs than for the pristine CNTs. The mechanism of the enhanced FE performance is discussed based on Schottky barrier effect.     

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.     

Effect of seed layer on the ferroelectric properties and leakage current characteristics of sol–gel derived vanadium doped PbZr0.53Ti0.47O3 films

In this paper, we report the ferroelectric properties and leakage current characteristics of vanadium-doped PbZr_0.53Ti_0.47O₃ (PZTV) films grown on various seed layers prepared by a sol–gel process. The PZTV multilayered film of ~250-nm-thick showed excellent ferroelectric properties, with a large remnant polarization (P _r) of ~30 μC/cm² (E _c ~ 90 kV/cm), a high saturation polarization (P _s) of ~85 μC/cm² for an applied field of 1,000 kV/cm, fatigue-free characteristics of up to ≥ 10¹⁰ switching cycles, and a low leakage current density of 7 × 10⁻⁸ A/cm² at 100 kV/cm. X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) investigations indicated that PZTV films grown on PbZr_0.53Ti_0.47O₃/PbLa_0.05TiO₃ (PZT/PLT) seed layers exhibited a dense, well-crystallized microstructure with random orientations and a rather smooth surface morphology.     

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.     

Fabrication and characterization of ferroelectric PLZT film capacitors on metallic substrates

We have grown ferroelectric Pb_0.92La_0.08Zr_0.52Ti_0.48O₃ (PLZT) films on Hastelloy C276 (HC) substrates by chemical solution deposition. Samples of 1.15-μm-thick PLZT films were prepared on HC with and without lanthanum nickel oxide (LNO) films as an intermediate buffer layer. On samples with and without LNO buffers at room temperature, we measured dielectric constants of ≈1,300 and ≈450 and loss tangents of ≈0.06 and ≈0.07, respectively. For PLZT films grown on HC with LNO buffer, the dielectric constant increases, while the dielectric loss decreases, with increasing temperature. A dielectric constant of ≈2,000 and loss of ≈0.05 were observed at 150 °C. Samples with LNO buffer also exhibited slimmer hysteresis loops and lower leakage current density when compared to samples without LNO buffer. The following results were measured on samples with and without LNO buffers: remanent polarization (P _r) values of 21.3 and 36.4 μC/cm², coercive electric field (E _c) values of 41 and 173 kV/cm, and leakage current densities of ≈1.1 × 10⁻⁸ and ≈1.6 × 10⁻⁷ A/cm², respectively. The energy storage capability was measured at ≈65 J/cm³ for the PLZT film-on-foil capacitor deposited on HC with LNO buffer.     

Study on electron field emission enhancement from nitrogenated carbon nanotips synthesized by plasma-enhanced hot filament chemical vapor deposition

Nitrogenated carbon nanotips (NCNTPs) with different structures were synthesized by plasma-enhanced hot filament chemical vapor deposition using methane, hydrogen and nitrogen as the reactive gases. The structures and compositions of the NCNTPs were studied by field emission scanning electron microscopy (FESEM), micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The XPS spectra reveal that nitrogen is incorporated into the carbon nanotips to form the NCNTPs under plasma condition. The Raman spectra and FESEM images show that the NCNTPs are amorphous structure and their morphologies change with the change in deposition conditions, respectively. The electron field emission (EFE) from the NCNTPs was measured and the EFE results indicate that the NCNTPs with the smooth surfaces and high density can emit a current density of 3 × 10³ μA/cm² at an electric field of 7.2 V/μm, which exhibits better EFE characteristic than the NCNTPs with the carbon nanowires on their surfaces due to small amount of oxygen adsorbed on the smooth surfaces of NCNTPs. According to the possible structures of nitrogen in sp² cluster in rings, the EFE enhancement of the NCNTPs compared with pure carbon nanotips was studied. The high emission current density (3 × 10³ μA/cm²) at low field (7.2 V/μm) suggests that the NCNTPs can serve as effective electron emission sources for numerous applications.