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Microstructural evolution of nanocrystalline diamond (NCD) nanoneedles owing to the addition of methane and nitrogen in the reactant gases is systematically addressed. It has been determined that varying the concentration of CH4in the CH4/H2/N2plasma is significant to tailor the morphology and microstructure of NCD films. While NCD films grown with 1% CH4in a CH4/H2/N2(3%) plasma contain large diamond grains, the microstructure changed considerably for NCD films grown using 5% (or 10%) CH4, ensuing in nanosized diamond grains. For 15% CH4-grown NCD films, a well-defined nanoneedle structure evolves. These NCD nanoneedle films contain sp3phase diamond, sheathed with sp2-bonded graphitic phases, achieving a low resistivity of 90 Ω cm and enhanced field electron emission (FEE) properties, namely, a low turn-on field of 4.3 V/μm with a high FEE current density of 3.3 mA/cm2(at an applied field of 8.6 V/μm) and a significant field enhancement factor of 3865. Furthermore, a microplasma device utilizing NCD nanoneedle films as cathodes can trigger a gas breakdown at a low threshold field of 3600 V/cm attaining a high plasma illumination current density of 1.14 mA/cm2at an applied voltage of 500 V, and a high plasma lifetime stability of 881 min is evidenced. The optical emission spectroscopy studies suggest that the C2, CN, and CH species in the growing plasma are the major causes for the observed microstructural evolution in the NCD films. However, the increase in substrate temperature to ∼780 °C due to the incorporation of 15% CH4in the CH4/H2/N2plasma is the key driver resulting in the origin of nanoneedles in NCD films. The outstanding optoelectronic characteristics of these nanoneedle films make them suitable as cathodes in high-brightness display panels.

An electron field emitter with superior electron field emission (EFE) properties and improved lifetime stability is being demonstrated via the combination of carbon nanotubes and the CH4/N2plasma grown ultrananocrystalline diamond (N-UNCD) films. The resistance of the carbon nanotubes to plasma ion bombardment is improved by the formation of carbon nanocones on the side walls of the carbon nanotubes, thus forming strengthened carbon nanotubes (s-CNTs). The N-UNCD films can thus be grown on s-CNTs, forming N-UNCD/s-CNTs carbon nanocomposite materials. The N-UNCD/s-CNTs films possess good conductivity of σ = 237 S/cm and marvelous EFE properties, such as low turn-on field of (E0) = 3.58 V/μm with large EFE current density of (Je) = 1.86 mA/cm2at an applied field of 6.0 V/μm. Moreover, the EFE emitters can be operated under 0.19 mA/cm2for more than 350 min without showing any sign of degradation. Such a superior EFE property along with high robustness characteristic of these combination of materials are not attainable with neither N-UNCD films nor s-CNTs films alone. Transmission electron microscopic investigations indicated that the N-UNCD films contain needle-like diamond grains encased in a few layers of nanographitic phase, which enhanced markedly the transport of electrons in the N-UNCD films. Moreover, the needle-like diamond grains were nucleated from the s-CNTs without the necessity of forming the interlayer that facilitate the transport of electrons crossing the diamond-to-Si interface. Both these factors contributed to the enhanced EFE behavior of the N-UNCD/s-CNTs films.

We improved the electron field emission properties of ultrananocrystalline diamond (UNCD) films grown on Si-tip arrays by using the carbon nanotubes (CNTs) as interlayer and post-treating the films in CH4/Ar/H2plasma. The use of CNTs interlayer effectively suppresses the presence of amorphous carbon in the diamond-to-Si interface that enhances the transport of electrons from Si, across the interface, to diamond. The post-treatment process results in hybrid-granular-structured diamond (HiD) films via the induction of the coalescence of the ultrasmall grains in these films that enhanced the conductivity of the films. All these factors contribute toward the enhancement of the electron field emission (EFE) process for the HiDCNT/Si-tipemitters, with low turn-on field of E0= 2.98 V/μm and a large current density of 1.68 mA/cm2at an applied field of 5.0 V/μm. The EFE lifetime stability under an operation current of 6.5 μA was improved substantially to τHiD/CNT/Si-tip= 365 min. Interestingly, these HiDCNT/Si-tipmaterials also show enhanced plasma illumination behavior, as well as improved robustness against plasma ion bombardment when they are used as the cathode for microplasma devices. The study concludes that the use of CNT interlayers not only increase the potential of these materials as good EFE emitters, but also prove themselves to be good microplasma devices with improved performance.

Enhanced electron field emission (EFE) properties due to hydrogen post-treatment at 600 °C have been observed for ultrananocrystalline diamond (UNCD) films. The EFE properties of H2-gas-treated UNCD films could be turned on at a low field of 5.3 V/μm, obtaining an EFE current density of 3.6 mA/cm2at an applied field of 11.7 V/μm that is superior to those of UNCD films treated with H2plasma. Transmission electron microscopic investigations revealed that H2plasma treatment induced amorphous carbon (a-C) (and graphitic) phases only on the surface region of the UNCD films but the interior region of the UNCD films still contained very small amounts of a-C (and graphitic) grain boundary phases, resulting in a resistive transport path and inferior EFE properties. On the other hand, H2gas treatment induces a-C (and graphitic) phases along the grain boundary throughout the thickness of the UNCD films, resulting in creation of conduction channels for the electrons to transport from the bottom of the films to the top and hence the superior EFE properties.

The enhanced lifetime stability for the carbon nanotubes (CNTs) by coating hybrid granular structured diamond (HiD) films on Au-decorated CNTs/Si using a two-step microwave plasma enhanced chemical vapor deposition process was reported. Electron field emission (EFE) properties of HiD/Au/CNTs emitters show a low turn-on field (E0) of 3.50 V/μm and a high emission current density (Je) of 0.64 mA/cm2at an applied field of 5.0 V/μm. There is no notable current degradation or fluctuation over a period of τHiD/Au/CNTs= 360 min for HiD/CNTs EFE emitters tested under a constant current of 4.5 μA. The robustness of the HiD/CNTs EFE emitter is overwhelmingly superior to that of bare CNTs EFE emitters (τCNTs= 30 min), even though the HiD/Au/CNTs do not show the same good EFE properties as CNTs, which are E0= 0.73 V/μm and Je= 1.10 mA/cm2at 1.05 V/μm. Furthermore, the plasma illumination (PI) property of a parallel-plate microplasma device fabricated using the HiD/Au/CNTs as a cathode shows a high Ar plasma current density of 1.76 mA/cm2at an applied field of 5600 V/cm with a lifetime of plasma stability of about 209 min, which is markedly better than the devices utilizing bare CNTs as a cathode. The CNT emitters coated with diamond films possessing marvelous EFE and PI properties with improved lifetime stability have great potential for the applications as cathodes in flat-panel displays and microplasma display devices.

Microstructural evolution of ultrananocrystalline diamond (UNCD) films in the bias-enhanced nucleation and growth (BEN-BEG) process in CH4/Ar plasma is systematically investigated. The BEN-BEG UNCD films possess higher growth rate and better electron field emission (EFE) and plasma illumination (PI) properties than those of the films grown without bias. Transmission electron microscopy investigation reveals that the diamond grains are formed at the beginning of growth for films grown by applying the bias voltage, whereas the amorphous carbon forms first and needs more than 30 min for the formation of diamond grains for the films grown without bias. Moreover, the application of bias voltage stimulates the formation of the nanographite phases in the grain boundaries of the UNCD films such that the electrons can be transported easily along the graphite phases to the emitting surface, resulting in superior EFE properties and thus leading to better PI behavior. Interestingly, the 10 min grown UNCD films under bias offer the lowest turn-on field of 4.2 V/μm with the highest EFE current density of 2.6 mA/cm2at an applied field of 7.85 V/μm. Such superior EFE properties attained for 10 min bias grown UNCD films leads to better plasma illumination (PI) properties, i.e., they show the smallest threshold field of 3300 V/cm with largest PI current density of 2.10 mA/cm2at an applied field of 5750 V/cm.

We report the systematic studies on the fabrication of aligned, uniform, and highly dense diamond nanostructures from diamond films of various granular structures. Self-assembled Au nanodots are used as a mask in the self-biased reactive-ion etching (RIE) process, using an O2/CF4process plasma. The morphology of diamond nanostructures is a close function of the initial phase composition of diamond. Cone-shaped and tip-shaped diamond nanostructures result for microcrystalline diamond (MCD) and nanocrystalline diamond (NCD) films, whereas pillarlike and grasslike diamond nanostructures are obtained for Ar-plasma-based and N2-plasma-based ultrananocrystalline diamond (UNCD) films, respectively. While the nitrogen-incorporated UNCD (N-UNCD) nanograss shows the most-superior electron-field-emission properties, the NCD nanotips exhibit the best photoluminescence properties, viz, different applications need different morphology of diamond nanostructures to optimize the respective characteristics. The optimum diamond nanostructure can be achieved by proper choice of granular structure of the initial diamond film. The etching mechanism is explained by in situ observation of optical emission spectrum of RIE plasma. The preferential etching of sp2-bonded carbon contained in the diamond films is the prime factor, which forms the unique diamond nanostructures from each type of diamond films. However, the excited oxygen atoms (O*) are the main etching species of diamond film.