Low threshold field electron emission from solvothermally synthesized WO2.72 nanowires

Field emission studies of WO_2.72 nanowires synthesized by a solvothermal method have been performed in the planar diode configuration under ultra high vacuum conditions. Fowler–Nordheim plots obtained from the current-voltage characteristics follow the quantum mechanical tunneling process and a current density of ∼8.3×10⁶ μA/cm² can be drawn at an applied electric field of 2 V/μm. The field enhancement factor is 33025, while the turn-on field is only 1.4 V/μm. The emission current-time plot recorded at the pre-set value of emission current of 1 μA over a period of more than 3 h exhibits an initial increase and a subsequent stabilization of the emission current. The results reveal that the WO_2.72 nanowire emitters synthesized by the solvothermal method are promising cathode materials for practical applications.     

Mechanism of field emission from carbon materials

Field emission in diamond and graphite-like polycrystalline films is investigated experimentally. It is shown that the emission efficiency increases as the nondiamond carbon phase increases; for graphite-like films the threshold electric field is less than 1.5 V/μm, and at 4 V/μm the emission current reaches 1 mA/cm², while the density of emission centers exceeds 10⁶ cm⁻². A general mechanism explaining the phenomenon of electron field emission from materials containing graphite-like carbon is proposed. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 1, 56–60 (10 July 1998)     

Electron field emission properties of conducting polymer coated multi walled carbon nanotubes

The present work describes the field emission characteristics of conducting polymer coated multi walled carbon nanotubes (MWNTs) field emitters fabricated over flexible graphitized carbon cloth. Nanocomposites involving the combination of MWNTs and conducting polymers polyaniline (PANI) and polypyrrole (PPy) have been prepared by in-situ polymerization method and have been characterized using scanning electron microscopy and transmission electron microscopy. Using spin coating method, field emitters based on PANI/MWNTs and PPy/MWNTs over flexible graphitized carbon cloth have been prepared. The field emission characteristics have been studied using an indigenously fabricated set up in a vacuum chamber with a base pressure of 2 × 10⁻⁵ Pa and the results are discussed. Our results display that the field emission performance of the emitters depends strongly on the work function of the emitting material. Low turn on emission field of 2.12 V/μm at 10 μA/cm² and high emission current density of 1 mA/cm² at 3.04 V/μm have been observed for PANI/MWNTs field emitter.     

Ultrahigh Electron Emissive Carbon Nanotubes with Nano-sized RuO2 Particles Deposition

Multi-wall carbon nanotubes (MWNTs) have a great commercial potential as electron field emitters, but suffer from fundamental problems such as stability and brightness. By depositing the MWNTs with nano-sized ruthenium dioxide (RuO₂) particles, a new high performance emitter has been developed. When compared to MWNTs, the MWNTs impregnated with 1–2 nm sized RuO₂ have superior and more efficient electrical characteristics. MWNTs supported by a silicon substrate showed a reduction in the onset voltage from 5.4 to 4 V/μm after RuO₂ impregnation. The long-term stability of the impregnated MWNTs is also demonstrated with only a 20% increase in applied voltage required after 700 h operation at 40 mA/cm².     

Synthesis of LaB6 micro/nano structures using picosecond (Nd:YAG) laser and its field emission investigations

Micro/nano structures have been obtained by laser surface treatment on sintered LaB₆ pellets employing a picosecond pulsed Nd:YAG laser at a pressure of ∼1×10⁻³ mbar. The X-ray diffraction pattern of the laser treated pellet shows a set of well defined diffraction peaks, indexed to the cubic phase of LaB₆ only. The scanning electron microscope studies reveal formation of micro and nano structures upon laser treatment and the resultant surface morphology is found to be strongly influenced by the laser fluence. Field electron emission studies made on the LaB₆ pellet, treated with optimized laser fluence, have been performed in a planar diode configuration under ultra high vacuum conditions. The threshold field required to draw an emission current density of ∼10 μA/cm² has been found to be ∼2.3 V/μm and a current density of ∼530 μA/cm² has been drawn at an applied field of 5.2 V/μm. The Fowler-Nordheim plot is found to be linear in accordance with the quantum mechanical tunneling phenomenon, confirming the metallic nature of the emitter. The emission current at the pre-set value ∼10 μA shows very good stability over a period of more than 3 hours. The present results emphasize the effectiveness of a picosecond laser treatment towards fabrication of a nano metric LaB₆ emitter for high current density applications.     

Growth and field emission properties of nanotip arrays of amorphous carbon with embedded hexagonal diamond nanoparticles

Nanotip arrays of amorphous carbon with embedded hexagonal diamond nanoparticles were prepared at room temperature for use as excellent field emitters by a unique combination of anodic aluminum oxide (AAO) template and filtered cathodic arc plasma (FCAP) technology. In order to avoid nanopore array formation on the AAO surface, an effective multi-step treatment employing anodization and pore-widening processes alternately was adopted. The nanotips were about 100 nm in width at the bottom and 150 nm in height with density up to 10¹⁰ cm⁻². Transmission electron microscopy investigation indicates that many nanoparticles with diameters of about 10 nm were embedded in the amorphous carbon matrix, which was proved to be hexagonal diamond phase by Raman spectrum and selected-area electron diffraction. There is no previous literature report on the field emission properties of hexagonal diamond and its preparation at room temperature under high-vacuum condition. The nanotip arrays with hexagonal diamond phase exhibit a low turn-on field of 0.5 V/μm and a threshold field of 3.5 V/μm at 10 mA/cm². It is believed that the existence of hexagonal diamond phase has improved the field emission properties.     

Vertically aligned carbon nanotubes from natural precursors by spray pyrolysis method and their field electron emission properties

Vertically aligned carbon nanotubes have been synthesized from botanical hydrocarbons: Turpentine oil and Eucalyptus oil on Si(100) substrate using Fe catalyst by simple spray pyrolysis method at 700°C and at atmospheric pressure. The as-grown carbon nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and Raman spectroscopy. It was observed that nanotubes grown from turpentine oil have better degree of graphitization and field emission performance than eucalyptus oil grown carbon nanotubes. The turpentine oil and eucalyptus oil grown carbon nanotubes indicated that the turn-on field of about 1.7 and 1.93 V/μm, respectively, at 10 μA/cm². The threshold field was observed to be about 2.13 and 2.9 V/μm at 1 mA/cm² of nanotubes grown from turpentine oil and eucalyptus oil respectively. Moreover, turpentine oil grown carbon nanotubes show higher current density in relative to eucalyptus oil grown carbon nanotubes. The maximum current density of 15.3 mA/cm² was obtained for ∼3 V/μm corresponding to the nanotubes grown from turpentine oil. The improved field emission performance was attributed to the enhanced crystallinity, fewer defects, and greater length of turpentine oil grown carbon nanotubes.     

Field electron emission of carbon-based nanocone films

Diamond nanocone, graphitic nanocone, and mixed diamond and graphitic nanocone films have been synthesized through plasma enhanced hot filament chemical vapor deposition (HFCVD). The field emission properties of these films have been experimentally investigated. The studies have revealed that all three kinds of nanocone films have excellent field electron emission (FEE) properties including low turn-on electric field and large emission current at low electric field. Compared with the diamond nanocone films (emission current of 86 μA at 26 V/μm with the turn-on field of 10 V/μm), the graphitic nanocone films exhibit higher FEE current of 1.8×10² μA at 13 V/μm and a lower turn-on filed of 4 V/μm. The mixed diamond and graphitic nanocone films have been found to posses FEE properties similar to graphitic nanocone films (emission current of 1.7×10² μA at 20 V/μm with the turn-on field of 5 V/μm), but have much better FEE stability than the graphitic nanocone films. PACS 81.07.Bc; 81.05.Uw; 79.70.+q     

Optimization of field emission properties from multi-walled carbon nanotubes using ceramic fillers

The field emission properties of multi-walled carbon nanotubes were examined using a screen-printed thick film with a diode-type configuration in a vacuum. The effects of various concentrations of two different ceramic fillers, indium tin oxide (ITO) powder and a glass frit, on the emission current density and turn-on field were evaluated. The emission properties of both pastes were dependent on the amount of filler. Considerably enhanced emission properties were obtained with the paste containing 5–10 wt.% of either ITO or the glass frit compared with those without a filler. The paste containing the ceramic filler showed enhanced emission properties compared with that containing the 5 wt.% Ag conventionally used, which confirmed the importance of the filler. The paste containing 10 wt.% ITO represented an emission current density of 176.4 μA/cm² at 5 V/μA, a turn-on field of 1.87 V/μA for an emission current density of 1 μA/cm² and a field enhancement factor of 7580. The paste formulation was also found to be suitable for fine patterning using UV-lithography techniques. A long-term stability test for 110 h of a paste containing 10 wt.% ITO revealed a half-life of approximately 30000 h, which is appropriate for commercial applications.     

Visible up-conversion and NIR luminescence studies of LiAl<Subscript>5</Subscript>O<Subscript>8</Subscript>:Er phosphor co-doped with Yb<Superscript>3+</Superscript> and Zn<Superscript>2+</Superscript>

The frequency up-conversion, an efficient laser emission and amplification in Er³⁺:LiAl₅O₈ phosphors co-doped with Yb³⁺ and Zn²⁺ phosphor powders in the 520–560, 640–680 nm regions and at ∼1.5 μm, respectively, have been reported. The emission corresponds to the ²H_11/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions upon direct excitation into the intermediated ⁴I_11/2 level using ∼980 nm radiation from a CW laser. Possible mechanisms involved for the up-conversion processes based on the energy level matching scheme, the pump-power dependence and the dynamical behaviour have been discussed. The effect of the addition of Yb³⁺ and Zn²⁺ for the amplification in the 1.5 μm eye-safe telecommunication window has been elaborated and characterized in detail.     

PLD synthesis of GaN nanowires and nanodots on patterned catalyst surface for field emission study

Patterned gallium nitride nanowires and nanodots have been grown on n-Si (100) substrates by pulsed laser deposition. The nanostructures are patterned using a physical mask, resulting in regions of nanowire growth of different densities. The field emission (FE) characteristics of the patterned gallium nitride nanowires show a turn-on field of 9.06 V/μm to achieve a current density of 0.01 mA/cm² and an enhanced field emission current density as high as 0.156 mA/cm² at an applied field of 11 V/μm. Comparing the peak FE current densities of both the nanowires and nanodots, the peak FE current density of nanowires is around 700 times higher than that of the peak FE current density of nanodots since nanodots have a lower aspect ratio compared to nanowires. The field emission results indicate that, besides density difference, crystalline quality as well as the low electron affinity of gallium nitride, high aspect ratio of gallium nitride nanostructures will greatly enhance their field emission properties.     

Spectroscopic properties of 1.8 μm emission of thulium ions in germanate glass

A new type host of germanate glass (GeO₂− BaO−BaF₂−Ga₂O₃−La₂O₃) codoped with Tm₂O₃ has been investigated for application as laser material. It possesses a large emission cross section with the value of 9.3×10⁻²¹ cm² at 1.8 μm. Judd-Ofelt intensity parameters and radiative transition probability are calculated and analyzed by Judd-Ofelt theory and absorption spectra. The infrared emission spectra at 1.8 μm have been obtained by using a 794 nm laser diode as excitation resource. The emission intensity ratio of 1.8 (³F₄→³H₆) to 1.47 μm (³H₄→³F₄) increases, while the experimental lifetime of the Tm³⁺:³H₄ level decreases by increasing Tm₂O₃ concentration, which is attributed to the presence of a cross relaxation process. The most intensive emission at 1.8 μm is achieved from the germanate glass with the concentration of Tm₂O₃ reaches 1.0 wt%. The extended overlap integral method is used to calculate the microparameter of the energy transfer and the critical distance, which are derived to better understand the energy transfer process of thulium ions in the germanate glass responsible for emission at 1.8 μm.     

Structure,transport and field-emission properties of compound nanotubes: CN<Subscript>x</Subscript> vs. BNC<Subscript>x</Subscript> (<Emphasis Type="Italic">x</Emphasis><0.1)

Transport and field-emission properties of as-synthesized CN_x and BNC_x (x<0.1) multi-walled nanotubes were compared in detail. Individual ropes made of these nanotubes and macrofilms of those were tested. Before measurements, the nanotubes were thoroughly characterized using high-resolution and energy-filtered electron microscopy, electron diffraction and electron-energy-loss spectroscopy. Individual ropes composed of dozens of CN_x nanotubes displayed well-defined metallic behavior and low resistivities of ∼10–100 kΩ or less at room temperature, whereas those made of BNC_x nanotubes exhibited semiconducting properties and high resistivities of ∼50–300 MΩ. Both types of ropes revealed good field-emission properties with emitting currents per rope reaching ∼4 μA(CN_x) and ∼2 μA (BNC_x), albeit the latter ropes se- verely deteriorated during the field emission. Macrofilms made of randomly oriented CN_x or BNC_x nanotubes displayed low and similar turn-on fields of ∼2–3 V/μm. 3 mA/cm² (BNC_x) and 5.5 mA/cm² (CN_x) current densities were reached at 5.5 V/μm macroscopic fields. At a current density of 0.2–0.4 mA/cm² both types of compound nanotubes exhibited equally good emission stability over tens of minutes; by contrast, on increasing the current density to 0.2–0.4 A/cm², only CN_x films continued to emit steadily, while the field emission from BNC_x nanotube films was prone to fast degradation within several tens of seconds, likely due to arcing and/or resistive heating. Received: 29 October 2002 / Accepted: 1 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Synthesis and field emission of diamond-like carbon nanorods on TiO2/Ti nanotube arrays

Highly ordered TiO₂/Ti nanotube arrays were fabricated by anodic oxidation method in 0.5 wt% HF. Using prepared TiO₂/Ti nanotube arrays deposited Ni nanoparticles as substrate, high quality diamond-like carbon nanorods (DLCNRs) were synthesized by a conventional method of chemical vapor deposition at 750 °C in nitrogen atmosphere. DLCNRs were analyzed by filed emission scanning electron microscopy and Raman spectrometer. It is very interesting that DLCNRs possess pagoda shape with the length of 3–10 μm. Raman spectra show two strong peaks about 1332 cm⁻¹ and 1598 cm⁻¹, indicating the formation of diamond-like carbon. The field emission measurements suggest that DLCNRs/TiO₂/Ti has excellent field emission properties, a low turn-on field about 3.0 V/μm, no evident decay at 3.4 mA/cm² in 480 min.     

Field emission from single-walled carbon nanotubes aligned on a gold plate using a self-assembly monolayer

Field emission from single-walled carbon nanotubes (SWNTs) aligned on a patterned gold surface is reported. The SWNT emitters were prepared at room temperature by a self-assembly monolayer technique. SWNTs were cut into sub-micron lengths by sonication in an acidic solution. Cut SWNTs were attached to the gold surface by the reaction between the thiol groups and the gold surface. The field-emission measurements showed that the turn-on field was 4.8 V/μm at an emission current density of 10 μA/cm². The current density was 0.5 mA/cm² at 6.6 V/μm. This approach provides a novel route for fabricating CNT-based field-emission displays. Received: 3 May 2002 / Accepted: 6 May 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +82-54/279-8298, E-mail: ce20047@postech.ac.kr     

Multiwalled carbon nanotubes mass-produced by dc arc discharge in He–H2 gas mixture

Uniform cathode deposits (longer than 15 mm), containing multiwalled carbon nanotubes (MWNTs) inside, were produced by dc arc discharge evaporation with a computer-controlled feeder of a pure-carbon electrode without a metal catalyst in a He–H₂ gas mixture. The purification of MWNTs was carried out to remove amorphous carbon and carbon nanoparticles. High-resolution transmission electron microscopy observations and Raman scattering studies show that the MWNTs possess a high crystallinity and a mean outermost diameter of ∼ ∼10 nm. It has been confirmed that the current density in the electron field emission from a purified MWNT mat can reach 77.92 mA/cm², indicating that the purified MWNTs are a promising candidate electron source in a super high-luminance light-source tube or a miniature X-ray source.     

Field-emission enhancement of molybdenum oxide nanowires with nanoprotrusions

The field-emission properties of molybdenum oxide nanowires grown on a silicon substrate and its emission performance in various vacuum gaps are reported in this article. A new kind of molybdenum oxides named nanowires with nanoscale protrusions on their surfaces were grown by thermal vapor deposition with a length of ~1 μm and an average diameter of ~50 nm. The morphology, structure, composition and chemical states of the prepared nanostructures were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). According to XRD, XPS, and TEM analyses, the synthesized samples were composed of MoO₂ nanowires formed over a thin layer of crystalline Mo₄O₁₁. TEM observation revealed that these nanowires have some nanoscale protrusion on their surface. These nanoprotrusions resulted in enhancement of field-emission properties of nanowires comprising nanoprotrusions. The turn-on emission field and the enhancement factor of this type of nanostructures were measured 0.2 V/μm and 42991 at the vacuum gap of 300 μm, respectively. These excellent emission properties are attributed to the special structure of the nanowires that have potential for utilizing in vacuum nanoelectronic and microelectronic applications.     

Field emission from lotiform-like ZnO nanostructures synthesized via thermal evaporation method

Novel lotiform ZnO nanostructures were synthesized on silicon substrate via simple thermal evaporation. The average diameter of the ZnO nanostructures is ∼1.5 μm. The lotiform-like ZnO structures were formed by nanorods arrays with the average diameter of 70 nm. The as-grown lotiform ZnO nanostructures have excellent field-emission properties such as the low turn-on field of 3.4 V/μm, and very high emission current density of 12.4 mA/cm² at the field of 9.6 V/μm. These features make the lotiform-like ZnO nanostructures competitive candidates for field-emission-based displays. PACS 61.46.-w; 61.82.Rx; 78.67.-n; 73.63.Bd; 74.78.Na     

Morphological effects on the field emission characteristics of zinc oxide nanotetrapods films

The direct growth of a tetrapod-like ZnO nanostructure has been accomplished by using a thermal oxidation method without any catalysts. Studies on the field emission properties of the ordered ZnO nanotetrapods films found that the shape of the ZnO nanotetrapods has considerable effect on their field emission properties, especially the turn-on field and the emission current density. Compared with the rod-like legs ZnO nanotetrapods, the nanotetrapods with acicular legs have a lower turn-on field of 2.7 V/μm at a current density of 10 μA/cm², a high field enhancement factor of 1830, and an available stability. More importantly, the emission current density reached 1 mA/cm² at a field of 4.8 V/μm without showing saturation. The results could be valuable for using the ZnO nanostructure as a cold-cathode field-emission material.      

Enhanced field emission from pulsed laser deposited nanocrystalline ZnO thin films on Re and W

Nanocrystalline ZnO thin films have been deposited on rhenium and tungsten pointed and flat substrates by pulsed laser deposition method. An emission current of 1 nA with an onset voltage of 120 V was observed repeatedly and maximum current density ∼1.3 A/cm² and 9.3 mA/cm² has been drawn from ZnO/Re and ZnO/W pointed emitters at an applied voltage of 12.8 and 14 kV, respectively. In case of planar emitters (ZnO deposited on flat substrates), the onset field required to draw 1 nA emission current is observed to be 0.87 and 1.2 V/μm for ZnO/Re and ZnO/W planar emitters, respectively. The Fowler–Nordheim plots of both the emitters show nonlinear behaviour, typical for a semiconducting field emitter. The field enhancement factor β is estimated to be ∼2.15×10⁵ cm⁻¹ and 2.16×10⁵ cm⁻¹ for pointed and 3.2×10⁴ and 1.74×10⁴ for planar ZnO/Re and ZnO/W emitters, respectively. The high value of β factor suggests that the emission is from the nanometric features of the emitter surface. The emission current–time plots exhibit good stability of emission current over a period of more than three hours. The post field emission surface morphology studies show no significant deterioration of the emitter surface indicating that the ZnO thin film has a very strong adherence to both the substrates and exhibits a remarkable structural stability against high-field-induced mechanical stresses and ion bombardment. The results reveal that PLD offers unprecedented advantages in fabricating the ZnO field emitters for practical applications in field-emission-based electron sources.