Enhanced second and third harmonic generations of vertical and planar spiral MoS2 nanosheets.

Molybdenum disulfide (MoS2), as one of the atomically thin two-dimensional transition metal dichalcogenides has novel layer-dependent optical and electronic properties, which make it competitive for potential applications in optoelectronics. Here, we report chemical vapor deposition growth of vertically-standing and planar spiral MoS2 nanosheets. These vertical spiral MoS2 nanosheets are formed by the compression between planar spiral MoS2 in a close proximity. Both structures have a polytype 3R stacking with broken inversion symmetry, exhibiting strong second and third harmonic generations.

Evolution of Irradiation-Induced Vacancy Defects in Boron Nitride Nanotubes.

Irradiation-induced vacancy defects in multiwalled (MW) boron nitride nanotubes (BNNTs) are investigated via in situ high-resolution transmission electron microscope operated at 80 kV, with a homogeneous distribution of electron beam intensity. During the irradiation triangle-shaped vacancy defects are gradually generated in MW BNNTs under a mediate electron current density (30 A cm(-2)), by knocking the B atoms out. The vacancy defects grow along a well-defined direction within a wall at the early stage as a result of the curvature induced lattice strain, and then develop wall by wall. The orientation or the growth direction of the vacancy defects can be used to identify the chirality of an individual wall. With increasing electron current density, the shape of the irradiation-induced vacancy defects changes from regular triangle to irregular polygon.

Boron Nitride Nanotubes: Recent Advances in Their Synthesis, Functionalization, and Applications.

A comprehensive overview of current research progress on boron nitride nanotubes (BNNTs) is presented in this article. Particularly, recent advancements in controlled synthesis and large-scale production of BNNTs will first be summarized. While recent success in mass production of BNNTs has opened up new opportunities to implement the appealing properties in various applications, concerns about product purity and quality still remain. Secondly, we will summarize the progress in functionalization of BNNTs, which is the necessary step for their applications. Additionally, selected potential applications in structural composites and biomedicine will be highlighted.

Progress in Electronic, Energy, Biomedical and Environmental Applications of Boron Nitride and MoS2 Nanostructures.

In this review, we examine recent progress using boron nitride (BN) and molybdenum disulfide (MoS2) nanostructures for electronic, energy, biomedical, and environmental applications. The scope of coverage includes zero-, one-, and two-dimensional nanostructures such as BN nanosheets, BN nanotubes, BN quantum dots, MoS2 nanosheets, and MoS2 quantum dots. These materials have sizable bandgaps, differentiating them from other metallic nanostructures or small-bandgap materials. We observed two interesting trends: (1) an increase in applications that use heterogeneous materials by combining BN and MoS2 nanostructures with other nanomaterials, and (2) strong research interest in environmental applications. Last, we encourage researchers to study how to remove nanomaterials from air, soil, and water contaminated with nanomaterials. As nanotechnology proceeds into various applications, environmental contamination is inevitable and must be addressed. Otherwise, nanomaterials will go into our food chain much like microplastics.

Origins of thermodynamically stable superhydrophobicity of boron nitride nanotubes coatings.

Superhydrophobic surfaces are attractive as self-cleaning protective coatings in harsh environments with extreme temperatures and pH levels. Hexagonal phase boron nitride (h-BN) films are promising protective coatings due to their extraordinary chemical and thermal stability. However, their high surface energy makes them hydrophilic and thus not applicable as water repelling coatings. Our recent discovery on the superhydrophobicity of boron nitride nanotubes (BNNTs) is thus contradicting with the fact that BN materials would not be hydrophobic. To resolve this contradiction, we have investigated BNNT coatings by time-dependent contact angle measurement, thermogravimetry, IR spectroscopy, and electron microscopy. We found that the wettability of BNNTs is determined by the packing density, orientation, length of nanotubes, and the environmental condition. The origins of superhydrophobicity of these BNNT coatings are identified as (1) surface morphology and (2) hydrocarbon adsorbates on BNNTs. Hydrocarbon molecules adsorb spontaneously on the curved surfaces of nanotubes more intensively than on flat surfaces of BN films. This means the surface energy of BNNTs was enhanced by their large curvatures and thus increased the affinity of BNNTs to adsorb airborne molecules, which in turn would reduce the surface energy of BNNTs and make them hydrophobic. Our study revealed that both high-temperature and UV-ozone treatments can remove these adsorbates and lead to restitution of hydrophilic BN surface. However, nanotubes have a unique capability in building a hydrophobic layer of adsorbates after a few hours of exposure to ambient air.

Field emission and strain engineering of electronic properties in boron nitride nanotubes.

The electrical properties of boron nitride (BN) nanostructures, particularly BN nanotubes (NTs), have been studied less in comparison to the counterpart carbon nanotubes. The present work investigates the field emission (FE) behavior of BNNTs under multiple cycles of FE experiments and demonstrates a strain-engineering pathway to tune the electronic properties of BNNTs. The electrical probing of individual BNNTs were conducted inside a transmission electron microscope (TEM) using an in situ electrical holder capable of applying a bias voltage of up to 110 V. Our results indicate that in the first cycle a single BNNT can exhibit the current density of ∼1 mA cm(-2) at 110 V and the turn-on voltage of 325 V µm(-1). However, field emission properties reduced considerably in subsequent cycles. Real-time imaging revealed the structural degradation of individual BNNTs during FE experiments. The electromechanical measurements show that the conductivity of BNNTs can be tuned by means of mechanical straining. The resistance of individual BNNTs reduced from 2000 to 769 MΩ and the carrier concentration increased from 0.35 × 10(17) to 1.1 × 10(17) cm(-3) by straining the samples up to 2.5%.

Low-temperature synthesis of indium tin oxide nanowires as the transparent electrodes for organic light emitting devices.

Low-temperature growth of indium tin oxide (ITO) nanowires (NWs) was obtained on catalyst-free amorphous glass substrates at 250 °C by Nd:YAG pulsed-laser deposition. These ITO NWs have branching morphology as grown in Ar ambient. As suggested by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM), our ITO NWs have the tendency to grow vertically outward from the substrate surface, with the (400) plane parallel to the longitudinal axis of the nanowires. These NWs are low in electrical resistivity (1.6×10⁻4 Ω cm) and high in visible transmittance (~90­96%), and were tested as the electrode for organic light emitting devices (OLEDs). An enhanced current density of ~30 mA cm⁻² was detected at bias voltages of ~19­21 V with uniform and bright emission. We found that the Hall mobility of these NWs is 2.2­2.7 times higher than that of ITO film, which can be explained by the reduction of Coulomb scattering loss. These results suggested that ITO nanowires are promising for applications in optoelectronic devices including OLED, touch screen displays, and photovoltaic solar cells.

Emerging Applications of Boron Nitride Nanotubes in Energy Harvesting, Electronics, and Biomedicine.

Boron nitride nanotubes (BNNTs) are structurally and mechanically similar to carbon nanotubes (CNTs). In contrast, BNNTs exhibit unique properties for being electrically insulating and optically transparent due to the polarized boron nitride bonds. All these properties have prevented the use of BNNTs for energy harvesting and electronic devices for more than 25 years. During the past few years, researchers have started to demonstrate a series of novel applications of BNNTs based on unique properties not found on CNTs. For example, these novel applications include osmotic power harvesting using the charged inner surfaces of BNNTs, room-temperature single-electron transistors using insulating BNNTs as the tunneling channels, high-brightness fluorophores that can be 1000-times brighter than regular dyes, and transistors based on Tellurium atomic chains filled inside BNNTs. We have reviewed some of these emerging applications and provided our perspective for future work.

Two-Dimensional Gold Quantum Dots with Tunable Bandgaps.

Metallic gold nanoparticles (Au NPs) with multilayer Au atoms are useful for plasmonic, chemical, medical, and metamaterial application. In this article, we report the opening of the bandgap in substrate-supported two-dimensional (2D) gold quantum dots (Au QDs) with monolayer Au atoms. Calculations based on density functional theory suggest that 2D Au QDs are energetically favorable over 3D Au clusters when coated on hexagonal boron nitride (BN) surfaces. Experimentally, we find that BN nanotubes (BNNTs) can be used to stabilize 2D Au QDs on their cylindrical surfaces as well as Au atoms, dimers, and trimers. The electrically insulating and optically transparent BNNTs enable the detection of the optical bandgaps of the Au QDs in the visible spectrum. We further demonstrate that the size and shapes of 2D Au QDs could be atomically trimmed and restructured by electron beam irradiation. Our results may stimulate further exploration of energetically stable, metal-based 2D semiconductors, with properties tunable atom by atom.

ZnO nanosquids: branching nanowires from nanotubes and nanorods.

One-dimensional (1D) semiconductor nanostructures are promising building blocks for future nanoelectronic and nanophotonic devices. ZnO has proven to be a multifunctional and multistructural nanomaterial with promising properties. Here we report the growth of ZnO nanosquids which can be directly grown on planar oxidized Si substrates without using catalysts and templates. The formation of these nanosquids can be explained by the theory of nucleation, and the vapor-solid crystal growth mechanism. The branching nanowires of these ZnO nanosquids could have potential application in multiplexing future nanoelectronic devices. The sharp band-edge emission at approximately 380 nm indicates that these ZnO nanosquids are also applicable for interesting optoelectronic devices.

Effect of graphitic order on field emission stability of carbon nanotubes.

We observed current density (J) dependent degradation in field emission current from multiwalled carbon nanotubes (MWCNTs). These degradations are recoverable and can be explained by emission current-induced dislocations along the MWCNTs. MWCNTs grown by thermal chemical vapour deposition (CVD) can emit stable current continuously for at least 1200 min with upper current density limits of approximately 0.5 mA cm(-2). In contrast, this upper limit is<40 microA cm(-2) for nanotubes grown by plasma-enhanced CVD (PECVD), although higher J is possible with relatively shorter stability duration. High-resolution transmission electron microscopy and Raman spectroscopy indicate higher graphitic order of the thermal CVD grown MWCNTs as compared to PECVD grown MWCNTs. Our study suggests that graphitic order affects their upper performance limits of long-term emission stability, although the effects from adsorbates cannot be completely ignored. These results indicate that field emission cannot be considered as an ideal quantum tunnelling process. The effect of electron transport along CNTs before electron tunnelling must be considered.

Surface-charge effects on the electro-orientation of insulating boron-nitride nanotubes in aqueous suspension.

The alignment of hexagonal boron-nitride nanotubes (BNNTs) in aqueous KCl solutions under spatially uniform electric fields was examined experimentally, using direct optical visualization to probe the orientation dynamics of individual BNNTs for different electric-field frequencies. Different from most previously studied nanowires and nanotubes, BNNTs are wide-bandgap materials which are essentially insulating at room temperature. We analyze the electro-orientation of BNNTs in the general context of polarizable cylindrical particles in liquid suspensions, whose behavior can fall into different regimes, including alignment due to Maxwell-Wagner induced dipoles at high frequencies, and alignment due to fluid motion of the electrical double layer around the particles at lower frequencies. For BNNTs, the variation of the crossover frequencies in the electro-orientation spectra was studied in electrolytes of different conductivity. The effect of BNNT surface charge on electro-orientation was further studied by changing the pH of the aqueous solution. We find that the electric-field alignment of the BNNTs in the low-frequency regime is associated with the charging and motion of the electrical double layer around the particle. However, as BNNTs are non-conducting particles, the reasons for the formation of the electrical double layer are likely to be different than that of conducting particles. We discuss two possible mechanisms for the double-layer formation and alignment of 1D dielectric particles, and make comparison to those for the more commonly studied conducting particles.

pH responsive controlled release of anti-cancer hydrophobic drugs from sodium alginate and hydroxyapatite bi-coated iron oxide nanoparticles.

Developing a drug carrier system which could perform targeted and controlled release over a period of time is utmost concern in the pharmaceutical industry. This is more relevant when designing drug carriers for poorly water soluble drug molecules such as curcumin and 6-gingerol. Development of a drug carrier system which could overcome these limitations and perform controlled and targeted drug delivery is beneficial. This study describes a promising approach for the design of novel pH sensitive sodium alginate, hydroxyapatite bilayer coated iron oxide nanoparticle composite (IONP/HAp-NaAlg) via the co-precipitation approach. This system consists of a magnetic core for targeting and a NaAlg/HAp coating on the surface to accommodate the drug molecules. The nanocomposite was characterized using FT-IR spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. The loading efficiency and loading capacity of curcumin and 6-gingerol were examined. In vitro drug releasing behavior of curcumin and 6-gingerol was studied at pH 7.4 and pH 5.3 over a period of seven days at 37°C. The mechanism of drug release from the nanocomposite of each situation was studied using kinetic models and the results implied that, the release is typically via diffusion and a higher release was observed at pH 5.3. This bilayer coated system can be recognized as a potential drug delivery system for the purpose of curcumin and 6-gingerol release in targeted and controlled manner to treat diseases such as cancer.

New Flexible Channels for Room Temperature Tunneling Field Effect Transistors.

Tunneling field effect transistors (TFETs) have been proposed to overcome the fundamental issues of Si based transistors, such as short channel effect, finite leakage current, and high contact resistance. Unfortunately, most if not all TFETs are operational only at cryogenic temperatures. Here we report that iron (Fe) quantum dots functionalized boron nitride nanotubes (QDs-BNNTs) can be used as the flexible tunneling channels of TFETs at room temperatures. The electrical insulating BNNTs are used as the one-dimensional (1D) substrates to confine the uniform formation of Fe QDs on their surface as the flexible tunneling channel. Consistent semiconductor-like transport behaviors under various bending conditions are detected by scanning tunneling spectroscopy in a transmission electron microscopy system (in-situ STM-TEM). As suggested by computer simulation, the uniform distribution of Fe QDs enable an averaging effect on the possible electron tunneling pathways, which is responsible for the consistent transport properties that are not sensitive to bending.

A Simple and Universal Technique To Extract One- and Two-Dimensional Nanomaterials from Contaminated Water.

We demonstrate a universal approach to extract one- and two-dimensional nanomaterials from contaminated water, which is based on a microscopic oil-water interface trapping mechanism. Results indicate that carbon nanotubes, graphene, boron nitride nanotubes, boron nitride nanosheets, and zinc oxide nanowires can be successfully extracted from contaminated water at a successful rate of nearly 100%. The effects of surfactants, particle shape, and type of organic extraction fluids are evaluated. The proposed extraction mechanism is also supported by in situ monitoring of the extraction process. We believe that this extraction approach will prove important for the purification of water contaminated by nanoparticles and will support the widespread adoption of nanomaterial applications.

Switching Behaviors of Graphene-Boron Nitride Nanotube Heterojunctions.

High electron mobility of graphene has enabled their application in high-frequency analogue devices but their gapless nature has hindered their use in digital switches. In contrast, the structural analogous, h-BN sheets and BN nanotubes (BNNTs) are wide band gap insulators. Here we show that the growth of electrically insulating BNNTs on graphene can enable the use of graphene as effective digital switches. These graphene-BNNT heterojunctions were characterized at room temperature by four-probe scanning tunneling microscopy (4-probe STM) under real-time monitoring of scanning electron microscopy (SEM). A switching ratio as high as 10(5) at a turn-on voltage as low as 0.5 V were recorded. Simulation by density functional theory (DFT) suggests that mismatch of the density of states (DOS) is responsible for these novel switching behaviors.

Very stable electron field emission from strontium titanate coated carbon nanotube matrices with low emission thresholds.

Novel PMMA-STO-CNT matrices were created by opened-tip vertically aligned multiwalled carbon nanotubes (VA-MWCNTs) with conformal coatings of strontium titanate (STO) and poly(methyl methacrylate) (PMMA). Emission threshold of 0.8 V/µm was demonstrated, about 5-fold lower than that of the as-grown VA-MWCNTs. This was obtained after considering the related band structures under the perspective of work functions and tunneling width as a function of the STO thickness. We showed that there is an optimum thickness of STO coatings to effectively reduce the work function of CNTs and yet minimize the tunneling width for electron emissions. Furthermore, simulation and modeling suggest that PMMA-STO-CNT matrices have suppressed screening effects and Coulombs' repulsion forces between electrons in adjacent CNTs, leading to low emission threshold, high emission density, and prolonged emission stability. These findings are important for practical application of VA-MWCNTs in field emission devices, X-ray generation, and wave amplification.

Diameter-dependent bending modulus of individual multiwall boron nitride nanotubes.

The mechanical properties of individual multiwall boron nitride nanotubes (MWBNNTs) synthesized by a growth-vapor-trapping chemical vapor deposition method are investigated by a three-point bending technique via atomic force microscopy. Multiple locations on suspended tubes are probed in order to determine the boundary conditions of the supported tube ends. The bending moduli (EB) calculated for 20 tubes with diameters ranging from 18 to 58 nm confirm the exceptional mechanical properties of MWBNNTs, with an average EB of 760 ± 30 GPa. For the first time, the bending moduli of MWBNNTs are observed to increase with decreasing diameter, ranging from 100 ± 20 GPa to as high as 1800 ± 300 GPa. This diameter dependence is evaluated by Timoshenko beam theory. The Young's modulus and shear modulus were determined to be 1800 ± 300 and 7 ± 1 GPa, respectively, for a trimmed data set of 16 tubes. The low shear modulus of MWBNNTs is the reason for the detected diameter-dependent bending modulus and is likely due to the presence of interwall shearing between the crystalline and faceted helical nanotube structures of MWBNNTs.

Room-temperature tunneling behavior of boron nitride nanotubes functionalized with gold quantum dots.

One-dimensional arrays of gold quantum dots (QDs) on insulating boron nitride nanotubes (BNNTs) can form conduction channels of tunneling field-effect transistors. We demonstrate that tunneling currents can be modulated at room temperature by tuning the lengths of QD-BNNTs and the gate potentials. Our discovery will inspire the creative use of nanostructured metals and insulators for future electronic devices.

Recent advancements in boron nitride nanotubes.

This article provides a concise review of the recent research advancements in boron nitride nanotubes (BNNTs) with a comprehensive list of references. As the motivation of the field, we first summarize some of the attractive properties and potential applications of BNNTs. Then, latest discoveries on the properties, applications, and synthesis of BNNTs are discussed. In particular, we focus on low-temperature and patterned growth, and mass production of BNNTs, since these are the major challenges that have hindered investigation of the properties and application of BNNTs for the past decade. Finally, perspectives of future research on BNNTs are discussed.