A simple combinatorial method aiding research on single-walled carbon nanotube growth on substrates

Establishing fabrication methods of carbon nanotubes (CNTs) is essential to realize many applications expected for CNTs. Catalytic growth of CNTs on substrates by chemical vapor deposition (CVD) is promising for direct fabrication of CNT devices, and catalyst nanoparticles play a crucial role in such growth. We have developed a simple method called "combinatorial masked deposition (CMD)", in which catalyst particles of a given series of sizes and compositions are formed on a single substrate by annealing gradient catalyst layers formed by sputtering through a mask. CMD enables preparation of hundreds of catalysts on a wafer, growth of single-walled CNTs (SWCNTs), and evaluation of SWCNT diameter distributions by automated Raman mapping in a single day. CMD helps determinations of the CVD and catalyst windows realizing millimeter-tall SWCNT forest growth in 10 min, and of growth curves for a series of catalysts in a single measurement when combined with realtime monitoring. A catalyst library prepared using CMD yields various CNTs, ranging from individuals, networks, spikes, and to forests of both SWCNTs and multi-walled CNTs, and thus can be used to efficiently evaluate self-organized CNT field emitters, for example. The CMD method is simple yet effective for research of CNT growth methods. © 2010 The Japan Society of Applied Physics.

Graphene-passivated nickel as an oxidation-resistant electrode for spintronics.

We report on graphene-passivated ferromagnetic electrodes (GPFE) for spin devices. GPFE are shown to act as spin-polarized oxidation-resistant electrodes. The direct coating of nickel with few layer graphene through a readily scalable chemical vapor deposition (CVD) process allows the preservation of an unoxidized nickel surface upon air exposure. Fabrication and measurement of complete reference tunneling spin valve structures demonstrate that the GPFE is maintained as a spin polarizer and also that the presence of the graphene coating leads to a specific sign reversal of the magneto-resistance. Hence, this work highlights a novel oxidation-resistant spin source which further unlocks low cost wet chemistry processes for spintronics devices.

Tantalum-oxide catalysed chemical vapour deposition of single- and multi-walled carbon nanotubes

Tantalum-oxide thin films are shown to catalyse single- and multi-walled carbon nanotube growth by chemical vapour deposition. A low film thickness, the nature of the support material (best results with SiO2) and an atmospheric process gas pressure are of key importance for successful nanotube nucleation. Strong material interactions, such as silicide formation, inhibit nanotube growth. In situ X-ray photoelectron spectroscopy indicates that no catalyst reduction to Ta-metal or Ta-carbide occurs during our nanotube growth conditions and that the catalytically active phase is the Ta-oxide phase. Such a reduction-free oxide catalyst can be technologically advantageous. © 2013 The Royal Society of Chemistry.

Fabrication and electrical integration of robust carbon nanotube micropillars by self-directed elastocapillary densification

Vertically aligned carbon nanotube (CNT) 'forest' microstructures fabricated by chemical vapor deposition (CVD) using patterned catalyst films typically have a low CNT density per unit area. As a result, CNT forests have poor bulk properties and are too fragile for integration with microfabrication processing. We introduce a new self-directed capillary densification method where a liquid is controllably condensed onto and evaporated from the CNT forests. Compared to prior approaches, where the substrate with CNTs is immersed in a liquid, our condensation approach gives significantly more uniform structures and enables precise control of the CNT packing density. We present a set of design rules and parametric studies of CNT micropillar densification by self-directed capillary action, and show that self-directed capillary densification enhances Young's modulus and electrical conductivity of CNT micropillars by more than three orders of magnitude. Owing to the outstanding properties of CNTs, this scalable process will be useful for the integration of CNTs as a functional material in microfabricated devices for mechanical, electrical, thermal and biomedical applications. © 2011 IOP Publishing Ltd.

Novel ZnO nanorod films by chemical solution deposition for planar device applications.

Smooth and continuous ZnO films consisting of densely packed ZnO nanorods (NRs), which can be used for electronic device fabrication, were synthesized using a hydro-thermo-chemical solution deposition method. Such devices would have the novelty of high performance, benefiting from the inherited unique properties of the nanomaterials, and can be fabricated on these smooth films using a conventional, low cost planar process. Photoluminescence measurements showed that the NR films have much stronger shallow donor to valence band emissions than those from discrete ZnO NRs, and hence have the potential for the development of ZnO light emission diodes and lasers, etc. The NR films have been used to fabricate large area surface acoustic wave devices by conventional photolithography. These demonstrated two well-defined resonant peaks and their potential for large area device applications. The chemical solution deposition method is simple, reproducible, scalable and economic. These NR films are suitable for large scale production on cost-effective substrates and are promising for various fields such as sensing systems, renewable energy and optoelectronic applications.

Structural and optical properties of III-V nanowires and nanowire heterostructures grown by metalorganic chemical vapour deposition

We have investigated the structural and optical properties of III-V nanowires grown by metalorganic chemical vapour deposition. Binary GaAs, InAs and InP nanowires, and ternary InGaAs and AlGaAs nanowires, have been fabricated and characterised. A variety of axial and radial heterostructures have also been fabricated, including GaAs/AlGaAs core-multishell and GaAs/InGaAs superlattice nanowires. GaAs/AlGaAs core-shell nanowires exhibit strong photoluminescence as the AlGaAs shell passivates the GaAs nanowire surface reducing the surface nonradiative recombination. © 2007 IEEE.

Structural and optical properties of axial and radial heterostructure III-V nanowires grown by metalorganic chemical vapour deposition

We have investigated the structural properties and photoluminescence of novel axial and radial heterostructure III-V nanowires, fabricated by metalorganic chemical vapour deposition. Segments of InGaAs have been incorporated within GaAs nanowires, to create axial heterostructure nanowires which exhibit strong photoluminescence. Photoluminescence is observed from radial heterostructure nanowires (core-shell nanowires), consisting of GaAs cores with AlGaAs shells. Core-multishell nanowires, of GaAs cores clad in several alternating layers of thick AlGaAs barrier shells and thin GaAs quantum well shells, exhibit a blue-shifted photoluminescence peak arising from quantum confinement effects. © 2006 Crown Copyright.

Optimised two-temperature growth of GaAs nanowire s by metalorganic chemical vapour deposition

We report a two-temperature procedure for the growth of GaAs nanowires by metalorganic chemical vapour deposition. An initial high temperature step affords effective nucleation and promotes epitaxial growth of straight (111)B-oriented nanowires. Lower temperatures are employed subsequently, to minimise nanowire tapering during growth. © 2006 IEEE.

Dry oxidation and vacuum annealing treatments for tuning the wetting properties of carbon nanotube arrays.

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.(1,2) These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.(2) Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.(3-5) The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

Band gap opening of graphene after UV/ozone and oxygen plasma treatments

Graphene grown by Chemical Vapor Deposition (CVD) on nickel subsrate is oxidized by means of oxygen plasma and UV/Ozone treatments to introduce bandgap opening in graphene. The degree of band gap opening is proportional to the degree of oxidation on the graphene. This result is analyzed and confirmed by Scanning Tunnelling Microscopy/Spectroscopy and Raman spectroscopy measurements. Compared to conventional wet-oxidation methods, oxygen plasma and UV/Ozone treatments do not require harsh chemicals to perform, allow faster oxidation rates, and enable site-specific oxidation. These features make oxygen plasma and UV/Ozone treatments ideal candidates to be implemented in high-throughput fabrication of graphene-based microelectronics. © 2011 Materials Research Society.

Photoluminescence and lasing properties of InAs/GaAs quantum dots grown by metal-organic chemical vapour deposition

Photoluminescence (PL) and lasing properties of InAs/GaAs quantum dots (QDs) with direrent growth procedures prepared by metalorganic chemical vapour deposition are studied. PL measurements show that the low growth rate QD sample has a larger PL intensity and a narrower PL line width than the high growth rate sample. During rapid thermal annealing, however, the lowgrowth rate sample shows a greater blue shift of PL peak wave length. This is caused by the larger InAs layer thickness which results from the larger 2-3 dimensional transition critical layer thickness for the QDs in the low-growth-rate sample. A growth technique including growth interruption and in-situ annealing, named indium flush method, is used during the growth of GaAs cap layer, which can flatten the GaAs surface effectively. Though the method results in a blue shift of PL peak wavelength and a broadening of PL line width, it is essential for the fabrication of room temperature working QD lasers.

Characterization of ZnMgO hexagonal-nanotowers/films on m-plane sapphire synthesized by metal organic chemical vapour deposition

ZnMgO hexagonal-nanotowers/films grown on m-plane sapphire substrates were successfully synthesized using a vertical low-pressure metal organic chemical vapour deposition system. The structural and optical properties of the as-obtained products were characterized using various techniques. They were grown along the non-polar [1 0 (1) over bar 0] direction and possessed wurtzite structure. The ZnMgO hexagonal-nanotowers were about 200 nm in diameter at the bottom and 120 nm in length. Photoluminescence and Raman spectra show that the products have good crystal quality with few oxygen vacancies. With Mg incorporation, multiple-phonon scattering becomes weak and broad, and the intensities of all observed vibrational modes decrease. The ultraviolet near band edge emission shows a clear blueshift (as much as 100 meV) and broadening compared with that of pure ZnO products.

A simple route of morphology control and structural and optical properties of ZnO grown by metal-organic chemical vapour deposition

Employing the metal-organic chemical vapour deposition (MOCVD) technique, we prepare ZnO samples with different morphologies from the film to nanorods through conveniently changing the bubbled diethylzinc flux (BDF) and the carrier gas flux of oxygen (OCGF). The scanning electron microscope images indicate that small BDF and OCGF induce two-dimensional growth while the large ones avail quasi-one-dimensional growth. X-ray diffraction (XRD) and Raman scattering analyses show that all of the morphology-dependent ZnO samples are of high crystal quality with a c-axis orientation. From the precise shifts of the 2 theta. locations of ZnO (002) face in the XRD patterns and the E-2(high) locations in the Raman spectra, we deduce that the compressive stress forms in the ZnO samples and is strengthened with the increasing BDF and OCGF. Photoluminescence spectroscopy results show all the samples have a sharp ultraviolet luminescent band without any defects-related emission. Upon the experiments a possible growth mechanism is proposed.