Boron and Nitrogen Co-Doped Porous Graphene Nanostructures for the Electrochemical Detection of Poisonous Heavy Metal Ions.

Heavy metal poisoning has a life-threatening impact on the human body to aquatic ecosystems. This necessitates designing a convenient green methodology for the fabrication of an electrochemical sensor that can detect heavy metal ions efficiently. In this study, boron (B) and nitrogen (N) co-doped laser-induced porous graphene (LIGBN) nanostructured electrodes were fabricated using a direct laser writing technique. The fabricated electrodes were utilised for the individual and simultaneous electrochemical detection of lead (Pb2+) and cadmium (Cd2+) ions using a square wave voltammetry technique (SWV). The synergistic effect of B and N co-doping results in an improved sensing performance of the electrode with better sensitivity of 0.725 µA/µM for Pb2+ and 0.661 µA/µM for Cd2+ ions, respectively. Moreover, the sensing electrode shows a low limit of detection of 0.21 µM and 0.25 µM for Pb2+ and Cd2+ ions, with wide linear ranges from 8.0 to 80 µM for Pb2+ and Cd2+ ions and high linearity of R2 = 0.99 in case of simultaneous detection. This rapid and facile method of fabricating heteroatom-doped porous graphene opens a new avenue in electrochemical sensing studies to detect various hazardous metal ions.

A Metal-Free Triazacoronene-Based Bimodal VOC Sensor.

Developing suitable sensors for selective and sensitive detection of volatile organic compounds (VOCs) is crucial for monitoring indoor and outdoor air quality. VOCs are very harmful to our health upon inhalation or contact. Bimodal sensor materials with more than one transduction capability (optical and electrical) offer the ability to extract complementary information from the individual analyte, thus improving detection accuracy and performance. The privilege of manipulating the optoelectronic properties of the polycyclic aromatic hydrocarbon-based semiconducting materials offers rapid signal transduction in multimodal sensing applications. A thiophene-functionalized triazacoronene (TTAC) donor-acceptor-donor (D-A-D) type sensor is reported here for VOC sensing. The single-crystal X-ray structure analysis of the TTAC revealed that a distinctive supramolecular polymer architecture was formed because of cooperative π-π and intermolecular D-A interactions and exhibited rapid signal transduction upon exposure to specific VOCs. The TTAC-embedded green luminescent paper-based test strip exhibited an on-off fluorescence response upon nitrobenzene vapor exposure for 120 s. The selective and rapid response is due to the fast photoinduced electron transfer, as is evident from the time-resolved excited-state dynamics and density functional theory studies. The thick-film-based prototype chemiresistive sensor detects harmful VOCs in a custom-made gas sensing system including benzene, toluene, and nitrobenzene. The TTAC sensor rapidly responds (200 s) at relatively low temperatures (180 οC) compared to other reported metal-oxide-based sensors.

Surfactant gel-based method: A universal soft method for the exfoliation of 2D materials.

HYPOTHESIS: Fluidic micelles and reverse micelles have served as exfoliation mediums. However, an additional force, such as extended sonication, is required. Gelatinous cylindrical micelles that are formed once desired conditions are achieved can be an ideal medium for the quick exfoliation of 2D materials without the need for any external force. The quick formation of gelatinous cylindrical micelles can rip off layers from the 2D materials suspended in the mixture leading to the quick exfoliation of 2D materials. EXPERIMENTS: Herein, we introduce a quick universal method capable of delivering high-quality exfoliated 2D materials cost-effectively using CTAB-based gelatinous micelles as an exfoliation medium. The approach is devoid of harsh treatment, such as prolonged sonication and heating, and a quick exfoliation of 2D materials is completed using this approach. FINDINGS: We successfully exfoliated four 2D materials (MoS2, Graphene, WS2, and BN) and investigated their morphology, chemical, and crystal structure along with optical and electrochemical properties to probe the quality of the exfoliated product. Results revealed that the proposed method is highly efficient in exfoliating 2D materials in a quick time without causing any significant damage to the mechanical integrity of the exfoliated materials.

Nitrogen-Incorporated Boron-Doped Nanocrystalline Diamond Nanowires for Microplasma Illumination.

The origin of nitrogen-incorporated boron-doped nanocrystalline diamond (NB-NCD) nanowires as a function of substrate temperature (Ts) in H2/CH4/B2H6/N2 reactant gases is systematically addressed. Because of Ts, there is a drastic modification in the dimensional structure and microstructure and hence in the several properties of the NB-NCD films. The NB-NCD films grown at low Ts (400 °C) contain faceted diamond grains. The morphology changes to nanosized diamond grains for NB-NCD films grown at 550 °C (or 700 °C). Interestingly, the NB-NCD films grown at 850 °C possess one-dimensional nanowire-like morphological grains. These nanowire-like NB-NCD films possess the co-existence of the sp3-diamond phase and the sp2-graphitic phase, where diamond nanowires are surrounded by sp2-graphitic phases at grain boundaries. The optical emission spectroscopy studies stated that the CN, BH, and C2 species in the plasma are the main factors for the origin of nanowire-like conducting diamond grains and the materialization of graphitic phases at the grain boundaries. Moreover, conductive atomic force microscopy studies reveal that the NB-NCD films grown at 850 °C show a large number of emission sites from the grains and the grain boundaries. While boron doping improved the electrical conductivity of the NCD grains, the nitrogen incorporation eased the generation of graphitic phases at the grain boundaries that afford conducting channels for the electrons, thus achieving a high electrical conductivity for the NB-NCD films grown at 850 °C. The microplasma devices using these nanowire-like NB-NCD films as cathodes display superior plasma illumination properties with a threshold field of 3300 V/µm and plasma current density of 1.04 mA/cm2 with a supplied voltage of 520 V and a lifetime stability of 520 min. The outstanding plasma illumination characteristics of these conducting nanowire-like NB-NCD films make them appropriate as cathodes and pave the way for the utilization of these materials in various microplasma device applications.

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.

Improved Field Electron Emission Properties of Phosphorus and Nitrogen Co-Doped Nanocrystalline Diamond Films.

Nanocrystalline diamond (NCD) field emitters have attracted significant interest for vacuum microelectronics applications. This work presents an approach to enhance the field electron emission (FEE) properties of NCD films by co-doping phosphorus (P) and nitrogen (N) using microwave plasma-enhanced chemical vapor deposition. While the methane (CH4) and P concentrations are kept constant, the N2 concentration is varied from 0.2% to 2% and supplemented by H2. The composition of the gas mixture is tracked in situ by optical emission spectroscopy. Scanning electron microscopy, atomic force microscopy (AFM), transmission electron microscopy, and Raman spectroscopy are used to provide evidence of the changes in crystal morphology, surface roughness, microstructure, and crystalline quality of the different NCD samples. The FEE results display that the 2% N2 concentration sample had the best FEE properties, viz. the lowest turn-on field value of 14.3 V/µm and the highest current value of 2.7 µA at an applied field of 73.0 V/µm. Conductive AFM studies reveal that the 2% N2 concentration NCD sample showed more emission sites, both from the diamond grains and the grain boundaries surrounding them. While phosphorus doping increased the electrical conductivity of the diamond grains, the incorporation of N2 during growth facilitated the formation of nano-graphitic grain boundary phases that provide conducting pathways for the electrons, thereby improving the FEE properties for the 2% N2 concentrated NCD films.

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.

High-performance supercabatteries using graphite@diamond nano-needle capacitor electrodes and redox electrolytes.

Supercabatteries have the characteristics of supercapacitors and batteries, namely high power and energy densities as well as long cycle life. To construct them, capacitor electrodes with wide potential windows and/or redox electrolytes are required. Herein, graphite@diamond nano-needles and an aqueous solution of Fe(CN)63-/4- are utilized as the capacitor electrode and the electrolyte, respectively. This diamond capacitor electrode has a nitrogen-doped diamond core and a nano-graphitic shell. In 0.05 M Fe(CN)63-/4- + 1.0 M Na2SO4 aqueous solution, the fabricated supercabattery has a capacitance of 66.65 mF cm-2 at a scan rate of 10 mV s-1. It is stable over 10 000 charge/discharge cycles. The symmetric supercabattery device assembled using a two-electrode system possesses energy and power densities of 10.40 W h kg-1 and 6.96 kW kg-1, respectively. These values are comparable to those of other energy storage devices. Therefore, diamond supercabatteries are promising for many industrial applications.

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.

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.

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.

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.

Highly Conductive Diamond-Graphite Nanohybrid Films with Enhanced Electron Field Emission and Microplasma Illumination Properties.

Bias-enhanced nucleation and growth of diamond-graphite nanohybrid (DGH) films on silicon substrates by microwave plasma enhanced chemical vapor deposition using CH4/N2 gas mixture is reported herein. It is observed that by controlling the growth time, the microstructure of the DGH films and, thus, the electrical conductivity and the electron field emission (EFE) properties of the films can be manipulated. The films grown for 30 min (DGHB30) possess needle-like geometry, which comprised of a diamond core encased in a sheath of sp(2)-bonded graphitic phase. These films achieved high conductivity of σ = 900 S/cm and superior EFE properties, namely, low turn-on field of 2.9 V/µm and high EFE current density of 3.8 mA/cm(2) at an applied field of 6.0 V/µm. On increasing the growth time to 60 min (the DGHB60), the acicular grain growth ceased and formed nanographite clusters or defective diamond clusters (n-diamond). Even though DGHB60 films possess higher electrical conductivity (σ = 1549 S/cm) than the DGHB30 films, the EFE properties degraded. The implication of this result is that higher conductivity by itself does not guarantee better EFE properties. The nanosized diamond grains with needle-like geometry are the most promising ones for the electron emission, exclusively when they are encased in graphene-like layers. The salient feature of such materials with unique granular structure is that their conductivity and EFE properties can be tuned in a wide range, which makes them especially useful in practical applications.

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.