Tensile properties of a boron/nitrogen-doped carbon nanotube–graphene hybrid structure

Doping is an effective approach that allows for the intrinsic modification of the electrical and chemical properties of nanomaterials. Recently, a graphene and carbon nanotube hybrid structure (GNHS) has been reported, which extends the excellent properties of carbon-based materials to three dimensions. In this paper, we carried out a first-time investigation on the tensile properties of the hybrid structures with different dopants. It is found that with the presence of dopants, the hybrid structures usually exhibit lower yield strength, Young’s modulus, and earlier yielding compared to that of a pristine hybrid structure. For dopant concentrations below 2.5% no significant reduction of Young’s modulus or yield strength could be observed. For all considered samples, the failure is found to initiate at the region where the nanotubes and graphene sheets are connected. After failure, monatomic chains are normally observed around the failure region. Dangling graphene layers without the separation of a residual CNT wall are found to adhere to each other after failure with a distance of about 3.4 Å. This study provides a fundamental understanding of the tensile properties of the doped graphene–nanotube hybrid structures, which will benefit the design and also the applications of graphene-based hybrid materials.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.

Neutral and charged boron-doped fullerenes for CO2 adsorption

Recently, the capture and storage of CO2 have attracted research interest as a strategy to reduce the global emissions of greenhouse gases. It is crucial to find suitable materials to achieve an efficient CO2 capture. Here we report our study of CO2 adsorption on boron-doped C60 fullerene in the neutral state and in the 1e−-charged state. We use first principle density functional calculations to simulate the CO2 adsorption. The results show that CO2 can form weak interactions with the BC59 cage in its neutral state and the interactions can be enhanced significantly by introducing an extra electron to the system.

Resonance of graphene nanoribbons doped with nitrogen and boron : a molecular dynamics study

Based on its enticing properties, graphene has been envisioned with applications in the area of electronics, photonics, sensors, bioapplications and others. To facilitate various applications, doping has been frequently used to manipulate the properties of graphene. Despite a number of studies conducted on doped graphene regarding its electrical and chemical properties, the impact of doping on the mechanical properties of graphene has been rarely discussed. A systematic study of the vibrational properties of graphene doped with nitrogen and boron is performed by means of a molecular dynamics simulation. The influence from different density or species of dopants has been assessed. It is found that the impacts on the quality factor, Q, resulting from different densities of dopants vary greatly, while the influence on the resonance frequency is insignificant. The reduction of the resonance frequency caused by doping with boron only is larger than the reduction caused by doping with both boron and nitrogen. This study gives a fundamental understanding of the resonance of graphene with different dopants, which may benefit their application as resonators.

Single-step, catalyst-free plasma-assisted synthesis and growth mechanism of single-crystalline aluminum nitride nanorods

Synthesis of one-dimensional AlN nanostructures commonly requires high process temperatures (>900 °C), metal catalyst, and hazardous gas/powder precursors. We report on a simple, single-step, catalyst-free, plasma-assisted growth of dense patterns of size-uniform single-crystalline AlN nanorods at a low substrate temperature (∼650 °C) without any catalyst or hazardous precursors. This unusual growth mechanism is based on highly effective plasma dissociation of N2 molecules, localized species precipitation on AlN islands, and reduced diffusion on the nitrogen-rich surface. This approach can also be used to produce other high-aspect-ratio oxide and nitride nanostructures for applications in energy conversion, sensing, and optoelectronics. © 2010 American Institute of Physics.

Controlled-bandgap silicon nitride nanomaterials : deterministic nitrogenation in high-density plasmas

To overcome major problems associated with insufficient incorporation of nitrogen in hydrogenated amorphous silicon nitride (a-SiNx:H) nanomaterials, which in turn impedes the development of controlled-bandgap nanodevices, here we demonstrate the possibility to achieve effective bandgap control in a broad range by using high-density inductively coupled plasmas. This achievement is related to the outstanding dissociation ability of such plasmas. It is shown that the compositional, structural, optical, and morphological properties of the synthesized a-SiNx:H nanomaterials can be effectively tailored through the manipulation of the flow rate ratio of the silane to nitrogen gases X. In particular, a wide bandgap of 5.21 eV can be uniquely achieved at a low flow rate ratio of the nitrogen to silane gas of 1.0, whereas typically used values often exceed 20.0. These results are highly-relevant to the development of the next-generation nanodevices that rely on the effective control of the functional nano-layer bandgap energies.

Inductively coupled plasma-assisted RF magnetron sputtering deposition of boron-doped microcrystalline Si films

An innovative custom-designed inductively coupled plasma-assisted RF magnetron sputtering deposition system has been developed to synthesize B-doped microcrystalline silicon thin films using a pure boron sputtering target in a reactive silane and argon gas mixture. Films were deposited using different boron target powers ranging from 0 to 350 W at a substrate temperature of 250 °C. The effect of the boron target power on the structural and electrical properties of the synthesized films was extensively investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and Hall-effect system. It is shown that, with an initial increase of the boron target power from 0 to 300 W, the structural and electrical properties of the B-doped microcrystalline films are improved. However, when the target power is increased too much (e.g. to 350 W), these properties become slightly worse. The variation of the structural and electrical properties of the synthesized B-doped microcrystalline thin films is related to the incorporation of boron atoms during the crystallization and doping of silicon in the inductively coupled plasma-based process. This work is particularly relevant to the microcrystalline silicon-based p-i-n junction solar cells.

Control and diagnostics of inductively coupled plasmas for chemical vapour deposition of nanocomposite carbon nitride-based films

Control and diagnostics of low-frequency (∼ 500 kHz) inductively coupled plasmas for chemical vapor deposition (CVD) of nano-composite carbon nitride-based films is reported. Relation between the discharge control parameters, plasma electron energy distribution/probability functions (EEDF/EEPF), and elemental composition in the deposited C-N based thin films is investigated. Langmuir probe technique is employed to monitor the plasma density and potential, effective electron temperature, and EEDFs/EEPFs in Ar + N2 + CH4 discharges. It is revealed that varying RF power and gas composition/pressure one can engineer the EEDFs/EEPFs to enhance the desired plasma-chemical gas-phase reactions thus controlling the film chemical structure. Auxiliary diagnostic tools for study of the RF power deposition, plasma composition, stability, and optical emission are discussed as well.

A non-aqueous solution synthesis of boron carbide by control of in-situ carbon

Synthesis of high quality boron carbide (B4C) powder is achieved by carbothermal reduction of boron oxide (B2O3) from a condensed boric acid (H3BO3) / polyvinyl acetate (PVAc) product. Precursor solutions are prepared via polymerisation of vinyl acetate (VA) in methanol in the presence of dissolved H3BO3. With excess VA monomer being removed during evaporation of the solvent, the polymerisation time is then used to manage availability of carbon for reaction.

Coherent phonon decay and the boron isotope effect for MgB2

Ab-initio DFT calculations for the phonon dispersion (PD) and the Phonon Density Of States (PDOS) of the two isotopic forms (10B and 11B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

In-situ carbon control in the preparation of precursors to boron carbide by a non-aqueous solution technique

Synthesis of high quality boron carbide (B4C) powders is achieved by carbothermal reduction of boron oxide (B2O3) from a condensed boric acid (H3BO3)/polyvinyl acetate (PVAc) product. Precursor solutions are prepared via free radical polymerisation of vinyl acetate (VA) monomer in methanol in the presence of dissolved H3BO3. A condensed product is then formed by flash evaporation under vacuum. As excess VA monomer is removed at the evaporation step, the polymerisation time is used to manage availability of carbon for reaction. This control of carbon facilitates dispersion of H3BO3 in solution due to the presence of residual VA monomer. B4C powders with very low residual carbon are formed at temperatures as low as 1,250 °C with a 4 hour residence time.

Synthesis, structure and properties elf a new ternary interstitial nitride: Ni2W3N

A new ternary interstitial nitride Ni2W3N has been synthesized by the ammonolysis of different oxide precursors and characterized by powder X-ray diffraction and electron microscopy. This nitride crystallizes in the cubic space group P4(1)32(213) [Ni2W3N, a=6.663(1) Angstrom, Z=4] and is isostructural with Al2Mo3C. This compound belongs to the rare class of intermetallic ternary nitrides and carbides crystallizing with a filled beta-Mn structure. Ni2W3N is not stable, it decomposes to a new compound NiW3N related to the distorted anti-perovskite, Ca3AsN structure.

Metal-free graphitic carbon nitride as mechano-catalyst for hydrogen evolution reaction

Graphitic carbon nitride (g-C3N4), as a promising metal-free catalyst for photo-catalytic and electrochemical water splitting, has recently attracted tremendous research interest. However, the underlying catalytic mechanism for the hydrogen evolution reaction (HER) is not fully understood. By using density functional theory calculations, here we have established that the binding free energy of hydrogen atom (ΔGH∗0) on g-C3N4 is very sensitive to mechanical strain, leading to substantial tuning of the HER performance of g-C3N4 at different coverages. The experimentally-observed high HER activity in N-doped graphene supported g-C3N4 (Zheng et al., 2014) is actually attributed to electron-transfer induced strain. A more practical strategy to induce mechanical strain in g-C3N4 is also proposed by doping a bridge carbon atom in g-C3N4 with an isoelectronic silicon atom. The calculated ΔGH∗0 on the Si-doped g-C3N4 is ideal for HER. Our results indicate that g-C3N4 would be an excellent metal-free mechano-catalyst for HER and this finding is expected to guide future experiments to efficiently split water into hydrogen based on the g-C3N4 materials.

Carbon nanodot decorated graphitic carbon nitride: New insights into the enhanced photocatalytic water splitting from ab initio studies

Interfacing carbon nanodots (C-dots) with graphitic carbon nitride (g-C3N4) produces a metal-free system that has recently demonstrated significant enhancement of photo-catalytic performance for water splitting into hydrogen [Science, 2015, 347, 970–974]. However, the underlying photo-catalytic mechanism is not fully established. Herein, we have carried out density functional theory (DFT) calculations to study the interactions between g-C3N4 and trigonal/hexagonal shaped C-dots. We find that hybrid C-dots/g-C3N4 can form a type-II van der Waals heterojunction, leading to significant reduction of band gap. The C-dot decorated g-C3N4 enhances the separation of photogenerated electron and hole pairs and the composite's visible light response. Interestingly, the band alignment of C-dots and g-C3N4 calculated by the hybrid functional method indicates that C-dots act as a spectral sensitizer in hybrid C-dots/g-C3N4 for water splitting. Our results offer new theoretical insights into this metal-free photocatalyst for water splitting.

Temperature measurements in the boron carbide manufacturing process - A hot model study

Boron carbide is produced in a heat resistance furnace using boric oxide and petroleum coke as the raw materials. The product yield is very low. Heat transfer plays an important role in the formation of boron carbide. Temperature at the core reaches up to 2600 K. No experimental study is available in the open literature for this high temperature process particularly in terms of temperature measurement and heat transfer. Therefore, a laboratory scale hot model of the process has been setup to measure the temperatures in harsh conditions at different locations in the furnace using various temperature measurement devices such as pyrometer and various types of thermocouple. Particular attention was paid towards the accuracy and reliability of the measured data. The recorded data were analysed to understand the heat transfer process inside the reactor and the effect of it on the formation of boron carbide.