Boron-Doped Nanocrystalline Diamond-Carbon Nanospike Hybrid Electron Emission Source.

Electron emission signifies an important mechanism facilitating the enlargement of devices that have modernized large parts of science and technology. Today, the search for innovative electron emission devices for imaging, sensing, electronics, and high-energy physics continues. Integrating two materials with dissimilar electronic properties into a hybrid material is an extremely sought-after synergistic approach, envisioning a superior field electron emission (FEE) material. An innovation is described regarding the fabrication of a nanostructured carbon hybrid, resulting from the one-step growth of boron-doped nanocrystalline diamond (BNCD) and carbon nanospikes (CNSs) by a microwave plasma-enhanced chemical vapor deposition technique. Spectroscopic and microscopic tools are used to investigate the morphological, bonding, and microstructural characteristics related to the growth mechanism of these hybrids. Utilizing the benefits of both the sharp edges of the CNSs and the high stability of BNCD, promising FEE performance with a lower turn-on field of 1.3 V/µm, a higher field enhancement factor of 6780, and a stable FEE current stability lasting for 780 min is obtained. The microplasma devices utilizing these hybrids as a cathode illustrate a superior plasma illumination behavior. Such hybrid carbon nanostructures, with superb electron emission characteristics, can encourage the enlargement of several electron emission device technologies.

Origin of Conductive Nanocrystalline Diamond Nanoneedles for Optoelectronic Applications.

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 CH4 in the CH4/H2/N2 plasma is significant to tailor the morphology and microstructure of NCD films. While NCD films grown with 1% CH4 in 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 sp3 phase 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/cm2 at 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% CH4 in the CH4/H2/N2 plasma 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.

Evolution of Granular Structure and the Enhancement of Electron Field Emission Properties of Nanocrystalline and Ultrananocrystalline Diamond Films Due to Plasma Treatment Process.

The present work reports the plasma post treatment (ppt) process that instigates the evolution of granular structure of nanocrystalline diamond (NCD), consequently conducing the enhancement of the electron field emission (EFE) properties. The NCD films contain uniform and nanosized diamond grains (∼20 nm) with negligible thickness for grain boundaries that is distinctly different from the microstructure of ultrananocrystalline (UNCD) films with uniformly sized ultrananodiamond grains (∼5 nm) having relatively thick grain boundaries (∼0.1 nm). The turn-on of the electron field emission (EFE) process occurs at ( E0)NCD = 24.1 V/µm and ( E0)UNCD = 18.6 V/µm for the pristine NCD and UNCD materials, respectively. The granular structure of the starting diamond films largely influenced the microstructure evolution behavior and EFE properties of the materials subject to plasma annealing. The CH4/(Ar-H2) ppt-process leads to formation of a hybrid granular structured diamond (HiDNCD and HiDUNCD) via isotropic conjoining of nanosized diamond grains, whereas the CH4/N2 ppt-process leads to the formation of acicular granular structured diamond films (NNCD and NUNCD) via inducing aeolotropic growth of nanodiamond grains. While both of the HiDNCD and HiDUNCD films contain hybrid granular structure, the HiDUNCD films contain a larger proportion of nanographite phase and result in improved EFE properties, viz. ( E0)HiD-UNCD = 7.7 V/µm and ( E0)HiD-NCD = 12.3 V/µm. In contrast, when the films were CH4/N2 ppt-processed, the acicular diamond grains were formed for NUNCD and NNCD films; however, carbon nanoclusters attached to the diamond grains of NNCD films and the nanographitic layers encasing diamond cores are not crystallized very well, as compared with NUNCD films. Therefore, the NNCD films exhibit slightly inferior EFE properties than the NUNCD films, viz. ( E0)N-UNCD = 5.3 V/µm and ( E0)N-NCD = 11.8 V/µm. The difference in EFE properties for ppt-processed NCD and UNCD films corresponds to the dissimilar granular structure evolution behavior in these films that is, in turn, due to the distinct different microstructure of the pristine NCD and UNCD films.

Self-organized multi-layered graphene-boron-doped diamond hybrid nanowalls for high-performance electron emission devices.

Carbon nanomaterials such as nanotubes, nanoflakes/nanowalls, and graphene have been used as electron sources due to their superior field electron emission (FEE) characteristics. However, these materials show poor stability and short lifetimes, which prevent their use in practical device applications. The aim of this study was to find an innovative nanomaterial possessing both high robustness and reliable FEE behavior. Herein, a hybrid structure of self-organized multi-layered graphene (MLG)-boron doped diamond (BDD) nanowall materials with superior FEE characteristics was successfully synthesized using a microwave plasma enhanced chemical vapor deposition process. Transmission electron microscopy reveals that the as-prepared carbon clusters have a uniform, dense, and sharp nanowall morphology with sp3 diamond cores encased by an sp2 MLG shell. Detailed nanoscale investigations conducted using peak force-controlled tunneling atomic force microscopy show that each of the core-shell structured carbon cluster fields emits electrons equally well. The MLG-BDD nanowall materials show a low turn-on field of 2.4 V µm-1, a high emission current density of 4.2 mA cm-2 at an applied field of 4.0 V µm-1, a large field enhancement factor of 4500, and prominently high lifetime stability (lasting for 700 min), which demonstrate the superiority of these materials over other hybrid nanostructured materials. The potential of these MLG-BDD hybrid nanowall materials in practical device applications was further illustrated by the plasma illumination behavior of a microplasma device with these materials as the cathode, where a low threshold voltage of 330 V (low threshold field of 330 V mm-1) and long plasma stability of 358 min were demonstrated. The fabrication of these hybrid nanowalls is straight forward and thereby opens up a pathway for the advancement of next-generation cathode materials for high brightness electron emission and microplasma-based display devices.

Microstructural Effect on the Enhancement of Field Electron Emission Properties of Nanocrystalline Diamond Films by Li-Ion Implantation and Annealing Processes.

The impact of lithium-ion implantation and postannealing processes on improving the electrical conductivity and field electron emission (FEE) characteristics of nitrogen-doped nanocrystalline diamond (nNCD) films was observed to be distinctly different from those of undoped NCD (uNCD) films. A high-dose Li-ion implantation induced the formation of electron trap centers inside the diamond grains and amorphous carbon (a-C) phases in grain boundaries for both types of NCD films. Postannealing at 1000 °C healed the defects, eliminated the electron trap centers, and converted the a-C into nanographitic phases. The abundant nanographitic phases in the grain boundaries of the nNCD films as compared to the uNCD films made an interconnected path for effectual electron transport and consequently enhanced the FEE characteristics of nNCD films.

Enhancement of plasma illumination characteristics of few-layer graphene-diamond nanorods hybrid.

Few-layer graphene (FLG) was catalytically formed on vertically aligned diamond nanorods (DNRs) by a high temperature annealing process. The presence of 4-5 layers of FLG on DNRs was confirmed by transmission electron microscopic studies. It enhances the field electron emission (FEE) behavior of the DNRs. The FLG-DNRs show excellent FEE characteristics with a low turn-on field of 4.21 V µm-1 and a large field enhancement factor of 3480. Moreover, using FLG-DNRs as cathode markedly enhances the plasma illumination behavior of a microplasma device, viz not only the plasma current density is increased, but also the robustness of the devices is improved.

Enhanced optoelectronic performances of vertically aligned hexagonal boron nitride nanowalls-nanocrystalline diamond heterostructures.

Field electron emission (FEE) properties of vertically aligned hexagonal boron nitride nanowalls (hBNNWs) grown on Si have been markedly enhanced through the use of nitrogen doped nanocrystalline diamond (nNCD) films as an interlayer. The FEE properties of hBNNWs-nNCD heterostructures show a low turn-on field of 15.2 V/µm, a high FEE current density of 1.48 mA/cm(2) and life-time up to a period of 248 min. These values are far superior to those for hBNNWs grown on Si substrates without the nNCD interlayer, which have a turn-on field of 46.6 V/µm with 0.21 mA/cm(2) FEE current density and life-time of 27 min. Cross-sectional TEM investigation reveals that the utilization of the diamond interlayer circumvented the formation of amorphous boron nitride prior to the growth of hexagonal boron nitride. Moreover, incorporation of carbon in hBNNWs improves the conductivity of hBNNWs. Such a unique combination of materials results in efficient electron transport crossing nNCD-to-hBNNWs interface and inside the hBNNWs that results in enhanced field emission of electrons. The prospective application of these materials is manifested by plasma illumination measurements with lower threshold voltage (370 V) and longer life-time, authorizing the role of hBNNWs-nNCD heterostructures in the enhancement of electron emission.

High Stability Electron Field Emitters Synthesized via the Combination of Carbon Nanotubes and N2-Plasma Grown Ultrananocrystalline Diamond Films.

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/N2 plasma 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 (J(e)) = 1.86 mA/cm(2) at an applied field of 6.0 V/µm. Moreover, the EFE emitters can be operated under 0.19 mA/cm(2) for 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.

Microstructural Evolution of Nanocrystalline Diamond Films Due to CH4/Ar/H2 Plasma Post-Treatment Process.

Plasma post-treatment process was observed to markedly enhance the electron field emission (EFE) properties of ultrananocrystalline diamond (UNCD) films. TEM examinations reveal that the prime factor which improves the EFE properties of these films is the coalescence of ultrasmall diamond grains (∼5 nm) forming large diamond grains about hundreds of nanometers accompanied by the formation of nanographitic clusters along the grain boundaries due to the plasma post-treatment process. OES studies reveal the presence of large proportion of atomic hydrogen and C2 (or CH) species, which are the main ingredients that altered the granular structure of the UNCD films. In the post-treatment process, the plasma interacts with the diamond films by a diffusion process. The recrystallization of diamond grains started at the surface region of the material, and the interaction zone increased with the post-treatment period. The entire diamond film can be converted into a nanocrystalline granular structure when post-treated for a sufficient length of time.

Role of carbon nanotube interlayer in enhancing the electron field emission behavior of ultrananocrystalline diamond coated Si-tip arrays.

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/H2 plasma. 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-tip emitters, with low turn-on field of E0 = 2.98 V/µm and a large current density of 1.68 mA/cm(2) at 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-tip materials 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.

Gold nanoparticle-ultrananocrystalline diamond hybrid structured materials for high-performance optoelectronic device applications.

Hybridization of gold nanoparticles in the ultrananocrystalline diamond materials improves the electrical conductivity of the materials to a high level of 230 (Ω cm)(-1) with a sheet carrier concentration of 8.9 × 10(20) cm(-2). These hybrid materials show enhanced electron field emission (EFE) properties, viz. a low turn-on field of 2.1 V µm(-1) with a high EFE current density of 5.3 mA cm(-2) (at an applied field of 4.9 V µm(-1)) and the life-time stability up to a period of 372 min. The fabrication of these hybrid materials with high conductivity and superior EFE behaviors is a direct and simple process which opens new prospects in flat panel displays and high brightness electron sources.

Enhancement of the electron field emission properties of ultrananocrystalline diamond films via hydrogen post-treatment.

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/cm(2) at an applied field of 11.7 V/µm that is superior to those of UNCD films treated with H2 plasma. Transmission electron microscopic investigations revealed that H2 plasma 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, H2 gas 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.

Enhancement of the stability of electron field emission behavior and the related microplasma devices of carbon nanotubes by coating diamond films.

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/cm(2) at an applied field of 5.0 V/µm. There is no notable current degradation or fluctuation over a period of τ(HiD/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 (τ(CNTs) = 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/cm(2) at 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/cm(2) at 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.

Bias-enhanced nucleation and growth processes for ultrananocrystalline diamond films in Ar/CH4 plasma and their enhanced plasma illumination properties.

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/cm(2) at 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/cm(2) at an applied field of 5750 V/cm.

Investigations on diamond nanostructuring of different morphologies by the reactive-ion etching process and their potential applications.

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/CF4 process 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 sp(2)-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.

Microplasma illumination enhancement of vertically aligned conducting ultrananocrystalline diamond nanorods.

Vertically aligned conducting ultrananocrystalline diamond (UNCD) nanorods are fabricated using the reactive ion etching method incorporated with nanodiamond particles as mask. High electrical conductivity of 275 Ω·cm-1 is obtained for UNCD nanorods. The microplasma cavities using UNCD nanorods as cathode show enhanced plasma illumination characteristics of low threshold field of 0.21 V/µm with plasma current density of 7.06 mA/cm2 at an applied field of 0.35 V/µm. Such superior electrical properties of UNCD nanorods with high aspect ratio potentially make a significant impact on the diamond-based microplasma display technology.

Low temperature synthesis of single-walled carbon nanotubes in an inductively coupled plasma chemical vapor deposition system.

In this work, we present a parametric study on the low temperature synthesis of single-walled carbon nanotubes (SWNTs) in an inductively coupled plasma (ICP) CVD system using dry bi-layered catalytic thin-films (Fe/Al and Ni/Al, deposited by electron-beam evaporation method) as the catalysts. With a low substrate temperature of 550 degrees C and above, SWNTs were successfully synthesized on both catalysts, as revealed from the characteristic peaks of SWNTs in the micro-Raman spectra. By the reduction of plasma power and the shortening of the process times, the lowest synthesis temperature of SWNTs achieved in our system was approached to 500 degrees C on Ni/Al catalysts; on the other hands, the lowest temperature for Fe/Al catalysts was 550 degrees C. Our results suggest that as compared with Fe/Al, Ni/Al is more favorable for plasma-enhanced CVD (PECVD) synthesis of SWNTs at low temperatures. This work can be used for further improvements and better understanding on the production processes of SWNTs by PECVD methods.

Direct synthesis of single-walled carbon nanotubes selectively suspended on tips of vertically aligned silicon nanostructures fabricated by hydrogen plasma etching.

Here we present a method to synthesize single-walled carbon nanotubes (SWNTs) selectively suspended on tips of silicon-based nanostructure (Si-ns) templates. The Si-ns templates vertically aligned to the substrates are fabricated via an anisotropic etch process using reactive hydrogen plasmas, in which the etch-resistive nanomasks are the nanosized particles formed by thermal annealing of multi-layered catalytic thin films. After plasma etching, the nanosized self-masks remaining at the tips of the Si-ns directly serve as the catalysts for SWNT growth by thermal chemical vapour deposition. Consequently, the synthesized SWNTs are selectively suspended on the tips of the Si-ns, as revealed by characterizations using scanning electron microscopy and resonance Raman spectroscopy. This methodology provides a simple and straightforward approach to assemble two different nanomaterials, i.e., Si-ns and suspended SWNTs, together as a building block for constructing nanodevices for possible applications.