Field emission characteristics of CNFB-CNT hybrid material grown by one-step MPCVD

A hybrid material consisting of carbon nanotubes (CNTs) and carbon nanoflake balls (CNFBs) was successfully synthesized by microwave-plasma-assisted chemical vapor deposition using a H₂/CH₄/N₂ ratio of 4:1:2 at 80 Torr for 30 min. The precursor used was a sol-gel solution containing ferric nitrate, tetrabutyl titanate, and n-propanol. The carbon hybrid material (CNFB-CNT) exhibited excellent field emission properties, with its turn-on field being 1.77 V/μm. It also showed two field enhancement factors (1536 and 7932) for different electric fields. The emission current density of the hybrid remained higher than 0.65 mA/cm² for more than 50 h and was 0.82 mA/cm² even after 50 h of continuous emission. Further, the field emission properties of the CNFB-CNT hybrid were better than those of other single-structured carbon nanomaterials (CNTs, CNFs, or CNFBs). Therefore, the CNFB-CNT hybrid material should be a promising candidate for use in high-performance field emitters.     

Electron field emission from filtered arc deposited diamond-like carbon films using Au and Ti layers

In this work, tetrahedral diamond-like carbon (DLC) films are deposited on Si, Ti/Si and Au/Si substrates by a new plasma deposition technique — filtered arc deposition (FAD). Their electron field emission characteristics and fluorescent displays of the films are tested using a diode structure. It is shown that the substrate can markedly influence the emission behavior of DLC films. An emission current of 0.1 μA is detected at electric field E_DLC/Si=5.6 V/μm, E_DLC/Au/Si=14.3 V/μm, and E_DLC/Ti/Si=5.2 V/μm, respectively. At 14.3 V/μm, an emission current density J_DLC/Si=15.2 μA/cm², J_DLC/Au/Si=0.4 μA/cm², and J_DLC/Ti/Si=175 μA/cm² is achieved, respectively. It is believed that a thin TiC transition layer exists in the interface between the DLC film and Ti/Si substrate.     

Growth and electron field emission properties of ultrananocrystalline diamond on silicon nanostructures

The electron field emission (EFE) properties of Si nanostructures (SiNS), such as Si nanorods (SiNR) and Si nanowire (SiNW) bundles were investigated. Additionally, ultrananocrystalline diamond (UNCD) growth on SiNS was carried out to improve the EFE properties of SiNS via forming a combined UNCD/SiNS structure. The EFE properties of SiNS were improved after the deposition of UNCD at specific growth conditions. The EFE performance of SiNR (turn-on field, E₀ = 5.3 V/μm and current density, J_e = 0.53 mA/cm² at an applied field of 15 V/μm) was better than SiNW bundles (turn-on field, E₀ = 10.9 V/μm and current density, J_e < 0.01 mA/cm² at an applied field of 15 V/μm). The improved EFE properties with turn-on field, E₀ = 4.7 V/μm, current density, J_e = 1.1 mA/cm² at an applied field of 15 V/μm was achieved for UNCD coated (UNCD grown for 60 min at 1200 W) SiNR. The EFE property of SiNW bundles was improved to a turn-on field, E₀ = 8.0 V/μm, and current density, J_e = 0.12 mA/cm² at an applied field of 15 V/μm (UNCD grown for 30 min at 1200 W).     

Electron field emission properties on UNCD coated Si-nanowires

The electron field emission (EFE) properties of Si-nanowires (SiNW) were improved by coating a UNCD films on the SiNWs. The SiNWs were synthesized by an electroless metal deposition (EMD) process, whereas the UNCD films were deposited directly on bare SiNW templates using Ar-plasma based microwave plasma enhanced chemical vapor deposition (MPE–CVD) process. The electron field emission properties of thus made nano-emitters increase with MPE–CVD time interval for coating the UNCD films, attaining small turn-on field (E₀ = 6.4 V/μm) and large emission current density (J_e = 6.0 mA/cm² at 12.6 V/μm). This is presumably owing to the higher UNCD granulation density and better UNCD-to-Si electrical contact on SiNWs. The electron field emission behavior of these UNCD nanowires emitters is significantly better than the bare SiNW ((E₀)_SiNWs = 8.6 V/μm and (J_e)_SiNWs < 0.01 mA/cm² at the same applied field) and is comparable to those for carbon nanotubes.     

Time dependent growth of ZnO nanoflowers with enhanced field emission properties

Herein, we report the facile growth of ZnO nanoflowers composed of nanorods on silicon substrate by non-catalytic thermal evaporation process. The grown nanoflowers were examined in terms of their morphological, structural, optical and field emission properties. The detailed characterizations revealed that the nanoflowers are grown in high density, possessing well-crystallinity and exhibiting wurtzite hexagonal phase. The Raman-scattering spectrum shows a sharp optical-phonon E₂ mode at 437 cm⁻¹ which confirmed the wurtzite hexagonal phase for the grown nanoflowers. The room-temperature PL spectrum depict a strong ultraviolet emission at 381 nm, revealed good optical properties for the ZnO nanoflowers. The field emission studies revealed that a turn-on field for the ZnO nanoflowers based field emission device was 4.3 V/μm and the emission current density reached to 0.075 mA/cm² at an applied electric field of 7.2 V/μm and exhibit no saturation. The field enhancement factor ‘β’ for the fabricated device was estimated from the F-N plot and found to be ~2.75×10³. Finally, systematic time-dependent experiments were performed to determine the growth process for the formation of ZnO nanoflowers composed of nanorods.     

The stability of the CNT/Ni field emission cathode fabricated by the composite plating method

A novel composite plating method has been developed for the fabrication of carbon nanotube/Ni (CNT/Ni) field emission cathode. The field emission properties of the initial CNT/Ni field emitter show a low turn-on electric field E_on of about 1.1 V/μm with an emission current density of 1 μA/cm², and a low threshold electric field E_th of about 1.7 V/μm with an emission current density of 1 mA/cm². After performing a stability test with a high emission current density in high vacuum, the corresponding microstructure and the degree of graphitization of the CNT/Ni field emitter were measured by using scanning electron microscopy and Raman spectroscopy. We found that the degree of graphitization slowly decreases with the duration time t_FE of the stability test, the size of small rod-like CNT/Ni composite structures in the film increases with t_FE, and obvious cracks appear in the film as t_FE is larger than 60 h. The degradation of the field emission properties may be explained by the Joule heating effect on the CNT/Ni field emitter under high emission current density.     

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.     

Long-term stability of a horizontally-aligned carbon nanotube field emission cathode coated with a metallic glass thin film

A horizontally-aligned carbon nanotube (HACNT) field emission cathode was coated with a metallic glass thin film (MGTF) to improve the stability of the field emission properties. HACNT field emission cathodes have previously been fabricated on glass substrates using composite plating and crack-formation techniques. A carbon nanotubes/nickel (CNTs/Ni) composite film is deposited onto a glass substrate at 80 °C by the composite plating technique alone. Cracks are then formed in the CNT/Ni composite film during 30 min heating at 300 °C, and HACNTs are exposed in the cracks. The field emission properties of the HACNT field emission cathode show a low turn-on electric field E_on of about 2.3 V/μm, a low threshold electric field E_th of about 4.7 V/μm at an emission current density of 1 mA/cm², and a stability time of 78 h. The degradation of the HACNT field emission cathode is prevented by using a MGTF-coating technique and superior long-term stability (i.e. >125 h, with 5 nm MGTF; >270 h, with 10 nm MGTF) for the MGTF/HACNT field emission cathode is achieved.     

Improved field emission properties of carbon nanotubes decorated with Ta layer

The field emission (FE) properties of vertically aligned carbon nanotube (CNT) arrays having a surface decorated with Ta layer were investigated. The CNTs with 6 nm thickness of Ta decoration showed improved FE properties with a low turn-on field of 0.64 V/μm at 10 μA/cm², a threshold field of 1.06 V/μm at 1 mA/cm² and a maximum current density of 7.61 mA/cm² at 1.6 V/μm. After Ta decoration, the increased emission centres and/or defect sites on the surface of CNTs improved the field enhancement factor. The work function of CNTs with Ta decoration measured with ultraviolet photoelectron spectroscopy decreased from 4.74 to 4.15 eV with increasing Ta thickness of 0–6 nm. The decreased work function and increased field enhancement factor were responsible for the improved FE properties of the vertically aligned CNTs. Moreover, a significant hysteresis in the cycle-testing of the current density with rising and falling electric field process was observed and attributed to the adsorption/desorption effect, as confirmed by the photoelectron spectrum.     

Effect of H2/Ar plasma on growth behavior of ultra-nanocrystalline diamond films: The TEM study

Incorporation of H₂ species into Ar plasma was observed to markedly alter the microstructure of diamond films. TEM examinations indicate that, while the Ar/CH₄ plasma produced the ultrananocrystalline diamond films with equi-axed grains (~ 5 nm), the addition of 20% H₂ in Ar resulted in grains with dendrite geometry and the incorporation of 80% H₂ in Ar led to micro-crystalline diamond with faceted grains (~ 800 nm). Optical emission spectroscopy suggests that small percentage of H₂-species (< 20%) in the plasma leads to partially etching of hydrocarbons adhered onto the diamond clusters, such that the C₂-species attach to diamond surface anisotropically, forming diamond flakes, which evolve into dendrite geometry. In contrast, high percentage of H₂-species in the plasma (80%) can efficiently etch away the hydrocarbons adhered onto the diamond clusters, such that the C₂-species can attach to diamond surface isotropically, resulting in large diamond grains with faceted geometry. The field needed to turn on the electron field emission for diamond films increases from E₀ = 22.1 V/μm (J_e = 0.48 mA/cm² at 50 V/μm applied field) for 0% H₂ samples to E₀ = 78.2 V/μm (J_e < 0.01 mA/cm² at 210 V/μm applied field) for 80% H₂ samples, as the grains grow, decreasing the proportion of grain boundaries.     

Carbon nanotube loop arrays for low-operational power,high uniformity field emission with long-term stability

We present a rational field emitter array architecture composed of thin multi-walled carbon nanotube “loops” which simultaneously satisfies the important requirements for practical applications. We achieved low turn-on voltage (1.27 V/μm for 10 μA/cm² emission), high enhancement factor (2400), uniformity, and long-term emission stability exceeding 10,000 h at 1 mA/cm², where each of the values approaches or exceeds the highest reported values to date for field emission arrays.     

Substrate temperature effects on the electron field emission properties of nitrogen doped ultra-nanocrystalline diamond

For the purpose of improving the electron field emission properties of ultra-nanocrystalline diamond (UNCD) films, nitrogen species were doped into UNCD films by microwave plasma chemical vapor deposition (MPCVD) process at high substrate temperature ranging from 600° to 830 °C, using 10% N₂ in Ar/CH₄ plasma. Secondary ion mass spectrometer (SIMS) analysis indicates that the specimens contain almost the same amount of nitrogen, regardless of the substrate temperature. But the electrical conductivity increased nearly 2 orders of magnitude, from 1 to 90 cm^− 1 Ω^− 1, when the substrate temperature increased from 600° to 830 °C. The electron field emission properties of the films were also pronouncedly improved, that is, the turn-on field decreased from 20 V/μm to 10 V/μm and the electron field emission current density increased from less than 0.05 mA/cm² to 15 mA/cm². The possible mechanism is presumed to be that the nitrogen incorporated in UNCD films are residing at grain boundary regions, converting sp³-bonded carbons into sp²-bonded ones. The nitrogen ions inject electrons into the grain boundary carbons, increasing the electrical conductivity of the grain boundary regions, which improves the efficiency for electron transport from the substrate to the emission sites, the diamond grains.     

Fabrication and field emission properties of ultra-nanocrystalline diamond lateral emitters

Field emission characteristics of ultra-nanocrystalline diamond (UNCD) have recently caught much attraction due to its importance in technological applications. In this work, we have fabricated lateral-field emitters comprised of UNCD films, which were deposited in CH₄/Ar medium by microwave plasma-enhanced chemical vapor deposition method. The substrates, silicon-on-insulator (SOI) or SiO₂-coated silicon, were pre-treated by mixed-powders-ultrasonication process for forming diamond nuclei to facilitate the synthesis of UNCD films on these substrates. Lateral electron field emitters can thus be fabricated either on silicon-on-insulator (SOI) or silicon substrates. The lateral emitters thus obtained possess large field enhancement factor (β = 1500–1721) and exhibit good electron field emission properties, regardless of the substrate materials used. The electron field emission can be turned on at 5.25–5.50 V/μm, attaining 5500–6000 mA/mm² at 12.5 V/μm (100 V applied voltage).     

Arc synthesis of double-walled carbon nanotubes in low pressure air and their superior field emission properties

Double-walled carbon nanotubes (DWCNTs) have been effectively synthesized by direct current (DC) arc discharge in low pressure air using a mixture of Fe catalyst and FeS promoter. Compared with conventional arc methods, this method is easier to implement without using expensive high purity gas sources. A tip structural DWCNT film has been successfully fabricated by a mixing process of electrophoresis, electroplating and electrocorrosion. The field emission properties of tip structural nanotube film are significantly increased compared with DWCNT film fabricated by electrophoresis. The turn-on electric field E_to decreases from 1.25 to 0.92 V/μm, the low threshold electric field E_th decreases from 1.45 to 1.13 V/μm, and the field enhancement factor β increases from about 2210 to 4450. Meanwhile, this tip structural CNT film shows remarkably stable within 2% fluctuations for several hours. The high-performance emitter material and preparation technologies are both easy to scale up to large areas.     

Plasma post-treatment process for enhancing electron field emission properties of ultrananocrystalline diamond films

This paper demonstrated the plasma post-treatment (ppt) process for modifying the granular structure of ultrananocrystalline diamond (UNCD) films so as to improve their electron field emission (EFE) properties. The ppt-processed UNCD films exhibited improved EFE properties as turn-on field of E₀ = 7.0 V/μm (J_e = 0.8 mA/cm² at 17.8 V/μm). TEM investigation revealed that the prime factor, which enhanced the EFE properties of the UCND films, is the induction of nano-graphitic clusters due to the ppt-process. However, for achieving such a goal, the granular structure of the primary UNCD layer has to be relatively open. That is, the size of grains should be sufficiently small and the grain boundaries should be of considerable thickness, containing abundant hydro-carbon species. Such a simple and robust process for synthesizing conductive UNCD films is especially useful for practical applications.     

Field emission devices for advanced electronics comprised of lateral nanodiamond or carbon nanotube emitters

Nanocarbon-derived electron emission devices, specifically, nanodiamond lateral field emission diodes and gated carbon nanotube triodes are new configurations for robust nanoelectronic devices. These novel micro/nanostructures provide an alternative and efficient means of accomplishing electronics that are impervious to temperature and radiation. Nitrogen-incorporated nanocrystalline diamond has been lithographically micropatterned to utilize the material as an electron field emitter. Arrays of laterally arranged “finger-like” nanodiamond emitters constitute the cathode in a versatile diode configuration with small interelectrode separation. Nanodiamond lateral tip conditioning techniques are employed to improve emission and the subsequent device performance discussed. A low diode turn-on voltage of 7 V and a high emission current of 90 μA at an anode voltage of 70 V (electric field of ∼ 7 V/μm) is reported for the nanodiamond lateral device. Also, the development of a field emission triode amplifier based on aligned carbon nanotubes (CNTs) with low turn-on voltage and small gate leakage current, utilizing a dual-mask microfabrication process is reported. The2 × 20 μm CNT triode array displays a gate turn-on voltage of ∼ 44 V, and low gate currents less than 3% of the anode currents. The low gate leakage currents observed confirmed the effectiveness of the convex-shaped gated CNT emitter in alleviating the cathode-gate leakage problem that compromises the operation of a field emission triode.     

Excellent field emission characteristics from few-layer graphene–carbon nanotube hybrids synthesized using radio frequency hydrogen plasma sputtering deposition

The growth of few-layer graphene (FLG) on carbon nanotubes (CNTs) was realized by using radio frequency hydrogen plasma sputtering deposition. A defect nucleation mechanism and a two dimensional growth model of the FLG were proposed, and field emission characteristics of these FLG–CNT hybrids were studied. They show excellent field emission properties, with a low turn-on electric field (0.98 V/μm) and threshold field (1.51 V/μm), large field enhancement factor (～3980) and good stability behavior, which are much better than those of the as-grown CNT arrays. The sharp edges and the low work function of the hybrids are believed to be responsible for the improved field emission properties.     

Effect of substrate heating and microwave attenuation on the catalyst free growth and field emission of carbon nanotubes

Carbon nanotubes (CNTs) have been directly grown on Inconel 600 substrates by microwave plasma enhanced chemical vapor deposition without using any external catalyst. Grown CNTs were characterized by field emission scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy and field emission measurements. Characterization results show that field emission current density increases from 200 μA/cm² at ∼5.5 V/μm to 14.5 mA/cm² at ∼1.6 V/μA when substrate is heat-treated and incident microwave is attenuated before reaching it. Detailed characterization reveals that heat-treatment results in migration of Cr and Fe oxides towards the top surface which completely changes substrate morphology also. Microwave attenuation reduces reflection of microwaves from the substrate and increases residence time of the precursor over the substrate promoting high density growth of CNTs. The combination of these two process parameters resulted in growth of long, dense CNTs with bamboo-like defects that contributes to enhanced current density at lower applied field.     

Direct synthesis of carbon nanofibers on the surface of copper powder

A novel approach to synthesize carbon nanofibers (CNFs) directly on the surface of metal μm-sized particles to evenly disperse the carbon nanomaterials in a composite material was proposed. As a metal matrix, 5–10 μm copper particles were utilized. As a carbon source, C₂H₂, CH₄ and CO were examined. The best conditions were found to be in C₂H₂ (30 cm³/min) and H₂ (260 cm³/min) atmosphere at the temperature of 750 °C. The composites based on copper and CNFs prepared by vacuum hot pressing showed the increase in hardness from 35 to 60 kg/mm² almost retaining pure copper electrical properties.     

Nitrogen-doped diamond films selected-area deposition by the plasma-enhanced chemical vapor deposition process

The nitrogen-doped diamond films have been successfully synthesized by using urea as the nitrogen source. Selected-area deposition of diamond nuclei was formed by using a SiO₂ layer as the masking material. Diamond pads, around 9 μm in diameter, were obtained when the N-doped diamond films were deposited on these patterned diamond nuclei using the chemical vapor deposition process. An emission current density as high as 200 μA/cm², with a turn-on field of around 8 V/μm, was obtained. However, the diamond emitters broke down easily, which is ascribed to the localized melting of the substrate materials surrounding the diamond pads.