Large scale highly organized single-walled carbon nanotube networks for electrical devices

Large-scale room-temperature liquid-phase directed assembly of highly organized single-walled carbon nanotubes (SWNT) over large areas is demonstrated. The presented process utilizes lithographically patterned template to guide the fluidic self-assembly of SWNTs on a silicon-dioxide substrate. The width of these highly organized SWNT structures are in the micron range while their heights are in orders of nanometers. Room temperature electrical I–V characterization of these fabricated high coverage SWNT wires show linear ohmic behavior. The resistivity of these assembled SWNT network is in the order of 10⁻⁶ Ω m demonstrating their metallic characteristics during conductance. Scaling of the assembly processes on a wafer level with high yield is demonstrated. Our developed assembly process is compatible with complimentary metal oxide semiconductor (CMOS) processes and provides a simple and flexible way of building SWNT nanotube-based electronics in a large scale.     

The dynamics simulation of Ne atom injected into single-wall carbon nanotube

The dynamical processes of Ne atom injected into single-wall carbon nanotube (SWCNT) are modeled with molecular dynamics simulations. The threshold energies to encapsulate rare-gas atoms in SWCNT are presented. The range of tube radius for stable oscillation is revealed, which is independent of the type of carbon nanotubes. And the oscillatory frequency is sensitive to the change in the diameter, the length and chirality of the tube.     

Cumulative and continuous laser vaporization synthesis of single wall carbon nanotubes and nanohorns

The conditions for the scaled synthesis of single wall carbon nanotubes (SWNTs) and single wall carbon nanohorns (SWNHs) by laser vaporization at high temperatures are investigated and compared using in situ diagnostics. An industrial Nd:YAG laser (600 W, 1–500 Hz repetition rate) with tunable pulse widths (0.5–50 ms) is utilized to explore conditions for high-yield production. High-speed videography (50000 frames/s) of the laser plume and pyrometry of the target surface are correlated with ex situ high resolution transmission electron microscopy analysis of the products for pure carbon targets and carbon/catalyst targets to understand the effects of the processing conditions on the resulting nanostructures. Carbon is shown to self-assemble into single-wall nanohorn structures at rates of ∼1 nm/ms, which is comparable to the catalyst-assisted SWNT growth rates. Two regimes of laser ablation, cumulative ablation by multiple pulses and continuous ablation by individual pulses, were explored. Cumulative ablation with spatially overlapping 0.5-ms pulses is favorable for the high yield and production rate of SWNTs at ∼6 g/h while continuous ablation by individual long laser pulses (∼20 ms) at high temperatures results in the highest yield of SWNHs at ∼10 g/h. Adjustment of the laser pulse width is shown to control SWNH morphology.     

The use of calcination in exposing the entrapped Fe particles from multi-walled carbon nanotubes grown by chemical vapour deposition

Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy, X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

Synthesis of multi-wall carbon nanotubes by copper vapor laser

Synthesis of multi-wall carbon nanotubes in a 1473 K furnace using a copper vapor laser (CVL) is reported. The operating parameters of this laser, i.e. a high fluence at the focal point and an extremely high frequency of 10 kHz, distinguished it from common laser sources in the synthesis of CNTs. Therefore, the unexpected experimental findings, the formation of MWNTs instead of the generally reported SWNTs, would be verified by these two notable parameters. Electron microscopy beside Raman spectroscopy illustrates the presence of multi-wall carbon nanotubes in the resulting product.     

Synthesis of 3-dimensional periodic nanostructures in an interference field of UV laser light

In 2000, Campbell et al. (Nature 404:53, 2000) have shown that three-dimensional periodic nanostructures can be obtained from UV laser interference irradiation of photoresist for 6 nanosecond single pulse. We have developed a similar experiment for photolytic gas phase decomposition and for photopatternable organic–inorganic hybrid resins. Different steps in results, presently reported, were first to determine the characteristics of both the 3D interference pattern and interferometer to be associated to a CVD reactor and second to verify the mechanical stability of the set up confirmed with the structuration of a siloxane based methacrylic resins by UV polymerization and finally to grow periodic nanostructures by photolytic gas phase decomposition of chromyl chloride. The experimental results obtained so far indicate that, depending on the electromagnetic energy density, a vapor phase decomposition of chromyl chloride leads to periodic arrays of either Cr–O amorphous or Cr₂O₃ particles on glass and (001)TiO₂ substrates at room temperature.     

Structural transformation of MoO<Subscript>3</Subscript> nanobelts into MoS<Subscript>2</Subscript> nanotubes

The structural transformation of MoO₃ nanobelts into MoS₂ nanotubes using a simple sulfur source has been reported. This transformation has been extensively investigated using electron microscopic and spectroscopic techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), and energy-dispersive X-ray analysis (SEM-EDAX and TEM-EDX). The method described in this report will serve as a generic route for the transformation of other oxide nanostructures into the chalcogenide nanostructures.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Role of growth temperature on nanostructure and field emission properties of PLD thin carbon films

Thin carbon films have been deposited in vacuum (∼10⁻⁴ Pa) on Si substrates by pulsed laser ablation of a graphite target using a Nd:YAG laser operating in the near infrared region (λ=1064 nm). The samples have been deposited at different substrate temperatures (T _sub) ranging from room temperature (RT) to 800°C. X-ray diffraction analysis established the progressive formation of nanosized graphene structures as T _sub increased. In fact, film structure evolves from almost amorphous to nanostructured phase characterized by graphene layers oriented perpendicularly to the film plane. The film density, evaluated by X-ray reflectivity measurements, is strongly affected by T _sub. At RT the film density is similar to the graphite one, while it decreases at higher T _sub. The electrical properties of the samples have been characterized by field emission measurements. The parameters describing the emitter properties (threshold field E _th and field enhancement factor β) have been evaluated using variable anode-to-cathode distance method. Samples deposited at low T _sub have shown the best emission properties, presenting lower E _th and larger β values than those deposited at higher T _sub. This is mainly attributed to the sensible density variation, which is in competition with the slighter augment of mean nanoparticle size.     

Electroluminescence from ZnO nanowire-based p-GaN/n-ZnO heterojunction light-emitting diodes

Vertically aligned ZnO nanowires were successfully grown on the sapphire substrate by nanoparticle-assisted pulsed laser deposition (NAPLD), which were employed in fabricating the ZnO nanowire-based heterojunction structures. p-GaN/n-ZnO heterojunction light-emitting diodes (LEDs) with embedded ZnO nanowires were obtained by fabricating p-GaN:Mg film/ZnO nanowire/n-ZnO film structures. The current–voltage measurements showed a typical diode characteristic with a threshold voltage of about 2.5 V. Electroluminescence (EL) emission having the wavelength of about 380 nm was observed under forward bias in the heterojunction diodes and was intensified by increasing the applied voltage up to 30 V.     

Melt-mediated coalescence of solution-deposited ZnO nanoparticles by excimer laser annealing for thin-film transistor fabrication

Nanoparticle solutions are considered promising for realizing low cost printable high performance flexible electronics. In this letter, excimer laser annealing (ELA) was employed to induce melting of solution-deposited ZnO nanoparticles and form electrically conductive porous films. The properties of the films were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, DC conductance, and photoluminescence measurements. Thin-film field-effect transistors have been fabricated by ELA without the use of conventional vacuum or any high temperature thermal annealing processes. The transistors show n-type accumulation mode behavior with mobility greater than 0.1 cm²/V s and current on/off ratios of more than 10⁴. Optimization and control of the laser processing parameters minimized thermal impact on the substrate. This technique can be beneficial in the fabrication of metal oxide based electronics on heat sensitive flexible plastic substrates using low-cost, large-area solution processing combined with direct printing techniques.     

Spatial characterization of the laser-induced plasma plumes generated by IR CO2 pulsed laser on carbon targets

We have used ferrocene and paraffin wax as novel precursor and solvent for the growth of iron oxide nanoparticles. The proposed method of growth has several advantages over existing methods of growth using iron pentacarbonyl a precursor. Highly crystalline and monodispersed particles are obtained which assemble in two- and three-dimensional hexagonal closed packed superlattices. Growth kinetics has been studied by varying concentration of the precursor and time of growth. A phenomenological model has been proposed to explain the growth kinetics.     

The role of defects in chemical sensing properties of carbon nanotube films

The electrical resistance of 24 different carbon nanotube (CNT) thin film samples in blowing ambient air and 10 different analyte vapor environments was measured. The effects of the CNT growth method, different chemical treatments, ball milling, sample preparation conditions and Ar⁺-ion irradiation are compared. Significant differences in the response signal curves as a function of time in the case of the studied sensor/vapor combinations show the important role of the defect structure and attached functional groups in the chemical sensing properties of CNTs.     

Investigation of Schottky-Barrier carbon nanotube field-effect transistor by an efficient semi-classical numerical modeling

An efficient semi-classical numerical modeling approach has been developed to simulate the coaxial Schottky-barrier carbon nanotube field-effect transistor (SB-CNTFET). In the modeling, the electrostatic potential of the CNT is obtained by self-consistently solving the analytic expression of CNT carrier distribution and the cylindrical Poisson equation, which significantly enhances the computational efficiency and simultaneously present a result in good agreement to that obtained from the non-equilibrium Green's function (NEGF) formalism based on the first principle. With this method, the effects of the CNT diameter, power supply voltage, thickness and dielectric constant of gate insulator on the device performance are investigated.     

Simple fabrication of hexagonally well-ordered AAO template on silicon substrate in two dimensions

In this study, thin anodic aluminum oxide (AAO) templates both on silicon substrates (AAO template/SiO₂/Si) and Ti-coated silicon substrates (AAO template/Ti/SiO₂/Si) were developed for design of magnetic, electronic and optoelectronic devices, chemical sensors and chip-scale lithium-ion rechargeable microbatteries. Two types of AAO template were prepared by using a two-step anodization procedure. The templates were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The obtained thin AAO templates were approximately 50 nm in diameter and 700 nm in length with 80-nm interpore distances in a relatively large area of 6 cm². A barrier layer of the AAO templates was removed by a cathodic polarization method in KCl solution for several seconds. The current–time transient during removing the alumina barrier layer of the thin AAO template and the mechanism of electrochemical dissolution of the barrier layer are given in detail.     

Laser-assisted local patterning of ZnO-based spots for mirror-less lasing

ZnO is known as one of the best materials for the implementation of the random lasing effect, associated with mirror-less laser emission in a simultaneously amplifying and highly scattering medium. Normally, the fabrication of this medium requires a rather complicated procedure of deposition and thermal treatment of ZnO-based films on some specific substrates, yielding wurtzite-orientation ZnO nanocrystals. We demonstrate a rapid synthesis of highly efficient ZnO-based random lasing spots on a piece of Zn by employing the phenomenon of laser-induced air breakdown. Being ignited near the surface of a Zn target, plasma of the air breakdown serves as a local reactor to locally transform its properties and thus form a film of well-packed 20–40 nm ZnO nanospheres. Exhibiting extremely high amplification and scattering, this medium is capable of generating the random lasing effect within the exciton-based photoluminescent band.     

Ultrafast laser based “green” synthesis of non-toxic nanoparticles in aqueous solutions

Inorganic nanoparticles offer novel promising properties for biological sensing and imaging, as well as in therapeutics. However, these applications are often complicated by the possible toxicity of conventional nanomaterials, arising as a result of inadequate purification procedures of nanoparticles obtained via synthetic pathways using toxic or non-biocompatible substances. We review novel femtosecond laser-assisted methods, which enable the preparation of metal nanomaterials in clean, biologically friendly aqueous environment (“green” synthesis) and thus completely solve the toxicity problem. The proposed methods, including laser ablation and fragmentation, make possible the production of stable metal colloids of extremely small size (∼2 nm) with a low coefficient of variation (15–25%). Those nanoparticles exhibit unique surface chemistry and can be used for bio-imaging, cancer treatment and nanoparticle-enhanced Raman spectroscopy.     

Cross patterning on MgO based on dislocations using femtosecond laser irradiation

We show a unique technique to form dense dislocations locally inside a MgO single crystal with a rock-salt type structure using femtosecond (fs) laser irradiation. Cross-shaped patterns of micrometer size, originating from densely introduced dislocations, are formed spontaneously around the focal point. We controlled the three-dimensional propagation of the dislocations by adjusting the pulse energy of the fs laser and NA of objective lens. The technique may open up a new field of dislocation technology for optical applications.     

Optimization of field emission properties from multi-walled carbon nanotubes using ceramic fillers

The field emission properties of multi-walled carbon nanotubes were examined using a screen-printed thick film with a diode-type configuration in a vacuum. The effects of various concentrations of two different ceramic fillers, indium tin oxide (ITO) powder and a glass frit, on the emission current density and turn-on field were evaluated. The emission properties of both pastes were dependent on the amount of filler. Considerably enhanced emission properties were obtained with the paste containing 5–10 wt.% of either ITO or the glass frit compared with those without a filler. The paste containing the ceramic filler showed enhanced emission properties compared with that containing the 5 wt.% Ag conventionally used, which confirmed the importance of the filler. The paste containing 10 wt.% ITO represented an emission current density of 176.4 μA/cm² at 5 V/μA, a turn-on field of 1.87 V/μA for an emission current density of 1 μA/cm² and a field enhancement factor of 7580. The paste formulation was also found to be suitable for fine patterning using UV-lithography techniques. A long-term stability test for 110 h of a paste containing 10 wt.% ITO revealed a half-life of approximately 30000 h, which is appropriate for commercial applications.