Developing tiny-sized particles, different modification behaviors of gold atoms, and nucleating distorted particles.

The study of tiny-sized particles is beneficial in many ways. This has been the subject of many studies. The development of a tiny-sized particle depends on the attained dynamics of the atoms. In the development process of a tiny-sized particle, gold atoms must deal with different modification behaviors. Photons traveling along the air-solution interface also alter the characteristics of a developing tiny-sized particle. The electronic structures, modification behaviors, and attained dynamics of the atoms mainly contribute toward the development of tiny-sized particles. Energy under the supplied source and the local resulting forces collectively bind gold atoms. Both internally and externally driven dynamics influence the development process of different tiny-sized particles. Atoms in such developed tiny-sized particles do not experience the collective oscillations upon photons traveling along the air-solution interface. In the study of binding atoms, it is essential to consider the roles of both energy and force. Here, the development of tiny particles having different sizes presents a convincing discussion. Nucleating a distorted particle from the non-uniform amalgamation of tiny-sized particles is also discussed.

Hydrogenation of diamond nanowire surfaces for effective electrostatic charge storage.

We report a novel versatile method for writing charged areas on diamond nanowire (DNW) surfaces using an atomic force microscopy (AFM) tip. Transmission electron microscopy (TEM) investigations revealed the existence of abundant plate-like diamond aggregates, which were encased in layers of graphite, forming nano-sized diamond-graphite composites (DGCs) on DNW surfaces. These DGCs are the main feature, acting as charge-trapping centers and storing electrostatic charge. A hydrogenation process has been observed effectively enhancing the charge-trapping properties of these DNW materials. The effective charge trapping properties with hydrogenation are ascribed to the disintegration of the DGCs into smaller pieces, with an overall increase in the metallic nanographitic phase fractions in a dielectric diamond matrix. Moreover, the written charge on the surface can be easily modified, re-written, or completely erased, enabling application in diamond-based re-writable electronic devices. However, excessive hydrogenation degrades the charge-trapping properties, which is attributed to the etching of the DGCs from the surface. This study demonstrates the potential importance of a simple hydrogenation process in effective electrostatic charge trapping and storage for diamond related nanocarbon materials and the role of DGCs to further enhance it.

Single-step grown boron doped nanocrystalline diamond-carbon nanograss hybrid as an efficient supercapacitor electrode.

Direct synthesis of a nano-structured carbon hybrid consisting of vertically aligned carbon nanograsses on top of boron-doped nanocrystalline diamond is demonstrated and the carbon hybrid is further applied as an electrode material for the fabrication of supercapacitors. The hybrid film combines the dual advantages of sp2 (carbon nanograss) and sp3 (nanocrystalline diamond) bonded carbon, possessing not only the excellent electrical characteristics of sp2 carbon but also the exceptional electrochemical stability of sp3 carbon. As a result, the specific capacitance of the as-prepared hybrid material reaches up to 0.4 F cm-2, one of the highest reported in diamond-based supercapacitors. The entire electrochemical results exhibit enhanced electron transfer efficiency with remarkable stability of 95% of capacitance retention even after 10 000 cycles.

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.

Laser-Patternable Graphene Field Emitters for Plasma Displays.

This paper presents a plasma display device (PDD) based on laser-induced graphene nanoribbons (LIGNs), which were directly fabricated on polyimide sheets. Superior field electron emission (FEE) characteristics, viz. a low turn-on field of 0.44 V/µm and a large field enhancement factor of 4578, were achieved for the LIGNs. Utilizing LIGNs as a cathode in a PDD showed excellent plasma illumination characteristics with a prolonged plasma lifetime stability. Moreover, the LIGN cathodes were directly laser-patternable. Such superior plasma illumination performance of LIGN-based PDDs has the potential to make a significant impact on display technology.

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.

Low Temperature Synthesis of Lithium-Doped Nanocrystalline Diamond Films with Enhanced Field Electron Emission Properties.

Low temperature (350 °C) grown conductive nanocrystalline diamond (NCD) films were realized by lithium diffusion from Cr-coated lithium niobate substrates (Cr/LNO). The NCD/Cr/LNO films showed a low resistivity of 0.01 Ω·cm and excellent field electron emission characteristics, viz. a low turn-on field of 2.3 V/µm, a high-current density of 11.0 mA/cm² (at 4.9 V/m), a large field enhancement factor of 1670, and a life-time stability of 445 min (at 3.0 mA/cm²). The low temperature deposition process combined with the excellent electrical characteristics offers a new prospective for applications based on temperature sensitive materials.

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.

Tribological Properties of Ultrananocrystalline Diamond Films: Mechanochemical Transformation of Sliding Interfaces.

Improving the tribological properties of materials in ambient and high vacuum tribo-conditions is useful for inter-atmospheric applications. Highly-hydrogenated and less-hydrogenated ultrananocrystalline diamond (UNCD) films with distinct microstructural characteristics were deposited on Ti-6Al-4 V alloy, by optimizing the plasma conditions in the chemical vapor deposition. Both the UNCD films showed less friction coefficient in ambient atmospheric tribo-contact conditions due to the passivation. This provides chemical stability to UNCD films under the tribo-mechanical stressed conditions which limits the transferlayer formation and conversion of UNCD phase into graphitization/amorphization. However, in the high vacuum tribo-conditions, highly-hydrogenated UNCD films showed low friction value which gradually increased to the higher magnitude at longer sliding cycles. The low friction coefficient was indicative of passivation provided by the hydrogen network intrinsically present in the UNCD films. It gradually desorbs and the dangling bonds are progressively activated in the contact regime, leading to a gradual increase in the friction value. In contrast, less-hydrogenated UNCD films do not exhibit low friction regime in high vacuum conditions due to the lack of internal passivation. In this case, the conversion of UNCD to amorphized carbon structure in the wear tracks and amorphous carbon (a-C) tribofilm formation on ball scars were observed.

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.

Nanoscale investigation of enhanced electron field emission for silver ion implanted/post-annealed ultrananocrystalline diamond films.

Silver (Ag) ions are implanted in ultrananocrystalline diamond (UNCD) films to enhance the electron field emission (EFE) properties, resulting in low turn-on field of 8.5 V/µm with high EFE current density of 6.2 mA/cm2 (at an applied field of 20.5 V/µm). Detailed nanoscale investigation by atomic force microscopy based peak force-controlled tunneling atomic force microscopy (PF-TUNA) and ultra-high vacuum scanning tunneling microscopy (STM) based current imaging tunneling spectroscopy (CITS) reveal that the UNCD grain boundaries are the preferred electron emission sites. The two scanning probe microscopic results supplement each other well. However, the PF-TUNA measurement is found to be better for explaining the local electron emission behavior than the STM-based CITS technique. The formation of Ag nanoparticles induced abundant sp2 nanographitic phases along the grain boundaries facilitate the easy transport of electrons and is believed to be a prime factor in enhancing the conductivity/EFE properties of UNCD films. The nanoscale understanding on the origin of electron emission sites in Ag-ion implanted/annealed UNCD films using the scanning probe microscopic techniques will certainly help in developing high-brightness electron sources for flat-panel displays applications.

High-Performance Electron Field Emitters and Microplasma Cathodes Based on Conductive Hybrid Granular Structured Diamond Materials.

High-performance diamond electron field emitters (EFEs) with extremely low turn-on field (E0 = 1.72 V/µm) and high current density (1.70 mA/cm2 at an applied field of 3.86 V/µm) were successfully synthesized by using a modified two-step microwave plasma chemical deposition process. Such emitters possess EFE properties comparable with most of carbon- or semiconductor-based EFE materials, but with markedly better lifetime stability. The superb EFE behavior of these materials was achieved owing to the reduction in the diamond-to-Si interfacial resistance and the increase in the conductivity of the bulk diamond films (HBD-400 V) via the applications of high bias voltage during the preparation of the ultrananocrystalline diamond (UNCD) primary layer and the subsequent plasma post-treatment (PPT) process, respectively. The superior EFE properties along with enhanced robustness of HBD-400 V films compared with the existing diamond-based EFE materials rendered these materials of greater potential for applications in high brightness display and multifunctional microplasma.

Long term in vivo functional stability and encapsulation reliability of using ultra-nanocrystalline diamond as an insulating coating layer for implantable microchips.

Thin ultra-nanocrystalline diamond (UNCD) films were evaluated for their use as encapsulating coatings for long-term implantable microchips. The ex vivo hermetic properties of UNCD coatings of various thicknesses and their reaction with tissues in vivo were investigated. Leakage current tests showed that the ∼300 nm thick coatings grown on microchips in (1% H2) Ar/CH4 plasma for 2 hours rendered the surface electrochemically inactive, i.e., the microchips showed an extremely low leakage current density (1.3 × 10-4 A cm-2 at ±5 V). The tests simulate the human body environment ex vivo. Six months after the implantation of the chips in mice, the leakage current density of the thin O-UNCD-coated chips was approximately 7.76 × 10-5 A cm-2 at ±5 V, which is lower than that of chips with a UNCD coating of 1.53 µm thickness deposited for 12 hours (1.71 × 10-4 A cm-2 at ±5 V). These results indicate that the thin coatings can effectively protect the implant from degradation in vivo. Moreover, the relationship between the surface properties of the carbon-based implants and the foreign-body response they elicit was established. Our results strongly indicate that the formation of a fibrous capsule surrounding the implants depend on the surface features of the implants (i.e., roughness, surface area, surface energy, and amount of absorbed fibrinogen) and on the amount of cytokines or chemokines secreted by the host through acute and chronic foreign-body reactions. Finally, oxygen-terminated UNCDs are promising candidates for use as encapsulating coatings without any additional surface modification or functionalization. They exhibit good bioinertness and hermeticity, thus contributing to the direct long-term protection of implantable microelectronic devices from chemical attack by bodily fluids in a physiological environment.

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.

Heterogranular-Structured Diamond-Gold Nanohybrids: A New Long-Life Electronic Display Cathode.

In the age of hand-held portable electronics, the need for robust, stable and long-life cathode materials has become increasingly important. Herein, a novel heterogranular-structured diamond-gold nanohybrids (HDG) as a long-term stable cathode material for field-emission (FE) display and plasma display devices is experimentally demonstrated. These hybrid materials are electrically conductive that perform as an excellent field emitters, viz. low turn-on field of 2.62 V/µm with high FE current density of 4.57 mA/cm(2) (corresponding to a applied field of 6.43 V/µm) and prominently high lifetime stability lasting for 1092 min revealing their superiority on comparison with the other commonly used field emitters such as carbon nanotubes, graphene, and zinc oxide nanorods. The process of fabrication of these HDG materials is direct and easy thereby paving way for the advancement in next generation cathode materials for high-brightness FE and plasma-based display devices.

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.

Fast Photoresponse and Long Lifetime UV Photodetectors and Field Emitters Based on ZnO/Ultrananocrystalline Diamond Films.

We have designed photodetectors and UV field emitters based on a combination of ZnO nanowires/nanorods (ZNRs) and bilayer diamond films in a metal-semiconductor-metal (MSM) structure. The ZNRs were fabricated on different diamond films and systematic investigations showed an ultra-high photoconductive response from ZNRs prepared on ultrananocrystalline diamond (UNCD) operating at a lower voltage of 2 V. We found that the ZNRs/UNCD photodetector (PD) has improved field emission properties and a reduced turn-on field of 2.9 V µm(-1) with the highest electron field emission (EFE) by simply illuminating the sample with ultraviolet (UV) light. The photoresponse (Iphoto /Idark ) behavior of the ZNRs/UNCD PD exhibits a much higher photoresponse (912) than bare ZNRs (229), ZNRs/nanocrystalline diamond (NCD; 518), and ZNRs/microcrystalline diamond (MCD; 325) under illumination at λ=365 nm. A photodetector with UNCD films offers superior stability and a longer lifetime compared with carbon materials and bare ZNRs. The lifetime stability of the ZNRs/UNCD-based device is about 410 min, which is markedly superior to devices that use bare ZNRs (92 min). The ZNRs/UNCD PD possesses excellent photoresponse properties with improved lifetime and stability; in addition, ZNRs/UNCD-based UV emitters have great potential for applications such as cathodes in flat-panel displays and microplasma display devices.