Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.     

Temperature dependence of a nanoporous Pd film hydrogen sensor based on an AAO template on Si

In this study, hydrogen sensing properties of nanoporous Pd films based on Anodic Aluminium Oxide (AAO) templates grown on a silicon substrate have been investigated at various temperatures (25–100°C) and hydrogen concentrations (100–1000 ppm) to determine the temperature-sensitivity relationship. For this purpose, a hexagonally shaped AAO template of approximately 50 nm in diameter and 700 nm in length with 80 nm interpore distances was fabricated using two-step anodization of an Al film deposited on an n-type (100) oriented oxidized Si substrate. Then, the nanoporous surface of the AAO template was used as a substrate for supporting a nanoporous Pd film of an approximately thickness of 60 nm. The morphologies of the AAO template and Pd film coated on the AAO template were studied mainly by Scanning Electron Microscopy (SEM). Hydrogen sensing properties of the nanoporous Pd film were measured using a resistance transient method. It was found that the sensor response of the nanoporous Pd films on the AAO template was better than the traditional Pd thin film sensors, the sensitivity of the sensor was approximately 1.8% for 1000 ppm H₂, and the detection limit was lower than 100 ppm at room temperature. The highest sensitivity was measured at room temperature.     

Carbon nanotube diameter tuning using hydrogen amount and temperature on SiO2/Si substrates

Carbon nanotubes (CNTs) were grown on thin iron (Fe) films on SiO₂/Si substrates by chemical vapor deposition (CVD) at four different hydrogen (H₂)/methane (CH₄) ratios at temperatures ranging from 925 to 1000°C. The effects of temperature and the amount of hydrogen gas on the mean diameter at increasing temperature were examined. We demonstrated that the mean diameter and its distribution depend not only on temperature but also on the H₂ amount. We showed that increasing H₂ amount strongly affects the structure of CNTs, especially at high growth temperature; the mean diameter at 1000°C reduced from about 383 to 34 nm by increasing H₂ amount from 24 to 50 sccm. We observed that at high temperature growth the mean diameter was decreasing very fast initially with increasing H₂ amount suggesting the dominance of H₂ over the growth temperature. A decrease in the slope of diameter vs. H₂ amount with further increment in H₂ amount implied that the temperature was, then, deciding the CNT diameter through catalyst particle coarsening. The statistical analysis presented implies that the H₂ amount has to be adjusted according to the growth temperature for given CH₄ amount to keep CNT diameter under control, and the large diameter distributions at high temperature and high H₂ amount can be associated with the large variation in the catalyst particle sizes.     

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.     

Controlling growth and Raman spectra of individual suspended single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were prepared with ethanol chemical vapor deposition (CVD) on SiO₂ flat and pillar-patterned Si substrates. The effect of CVD temperatures from 600 to 800 °C on SWNTs yields was investigated. By virtue of its unperturbed environment, an individual suspended SWNT grown between two different SiO₂ pillars provides a possibility to study the phonon band structure of SWNT itself at a single-nanotube level. Raman spectra of individual SWNTs grown between pillars were investigated systematically.     

Fabrication of the uniform CdTe quantum dot array on GaAs substrate utilizing nanoporous alumina masks

Fabrication of quantum dot array (QDA) is attractive for applications in electronic and optoelectronic devices. The CdTe QDAs have potential applications in optoelectronic devices of visible range. One of the major challenges in fabricating QDAs is the uniformity and reproducibility in size and spatial distribution. The uniformity and reproducibility of QDs can be improved by using the nanoporous alumina mask. The geometry of porous alumina is schematically represented as a close-packed array of columnar hexagonal cells, each containing a central pore normal to the substrate. The well-ordered nanoporous alumina masks were able to obtain by two-step anodizing processes from aluminum in oxalic acid solutions at low temperature. The pore size, thickness, and density of nanoporous alumina mask can be controlled with the anodization voltage, time, and electrolyte. The CdTe QDAs on the GaAs substrate was grown by molecular beam epitaxy method using the porous alumina masks. The temperature of substrate and source (Cd, Te) was an important factor for the growth of CdTe QDs on GaAs substrate. The CdTe QDAs of 80 nm dot size was fabricated; using the porous alumina masks (300 nm thickness) of pore diameter (80 nm) and density (10¹⁰ /cm²).     

EDLC characteristics with high specific capacitance of the CNT electrodes grown on nanoporous alumina templates

Well-ordered nanoporous alumina templates were fabricated by two-step anodization method by applying a constant voltage of 40 V in oxalic acid solution or of 25 V in sulfuric acid solution. The cylindrical pore diameter and pore density of the templates utilized for the carbon nanotube (CNT) growth were 86 ± 5 nm and 1.2 × 10¹⁰ cm⁻² in oxalic acid solution and 53 ± 1 nm and 3.1 × 10¹⁰ cm⁻² in sulfuric acid solution, respectively. The CNTs with uniform diameter of 50 ± 10 nm (oxalic acid) and 44 ± 2 nm (sulfuric acid) were grown on the porous alumina template as electrode materials for the electrochemical double layer capacitor (EDLC). The EDLC characteristics were examined by measuring the capacitances from cyclic voltammograms and the charge–discharge curves. The specific capacitances of the CNT electrodes are 30 ± 1 F/g (Φ = 50 ± 10 nm) and 121 ± 5 F/g (Φ = 44 ± 2 nm). The high specific capacitance of the CNT electrode was achieved by using nanoporous alumina templates with the high pore density and the small and uniform pore diameter.     

Novel structure formation at the bottom surface of porous anodic alumina fabricated by single step anodization process

A simple approach for the growth of long-range highly ordered nanoporous anodic alumina film in H₂SO₄ electrolyte through a single step anodization without any additional pre-anodizing procedure is reported. Free-standing porous anodic alumina film of 180 μm thickness with through hole morphology was obtained. A simple and single step process was used for the detachment of alumina from aluminum substrate. The effect of anodizing conditions, such as anodizing voltage and time on the pore diameter and pore ordering is discussed. The metal/oxide and oxide/electrolyte interfaces were examined by high resolution scanning transmission electron microscope. The arrangement of pores on metal/oxide interface was well ordered with smaller diameters than that of the oxide/electrolyte interface. The inter-pore distance was larger in metal/oxide interface as compared to the oxide/electrolyte interface. The size of the ordered domain was found to depend strongly upon anodizing voltage and time.     

Controllable growth and characterization of isolated single-walled carbon nanotubes catalyzed by Co particles

Discrete Co catalytic nanoparticles with small diameters are obtained by pulsed vacuum arc evaporation on Si/SiO₂ substrates, which are used for the growth of isolated single-walled carbon nanotubes (SWNTs) by an ethanol chemical vapor deposition approach (CVD). The distributions of catalytic nanoparticles change with the number of arc pulses, which allows control of the nanotubes formation. We find that an increase of ethanol pressure during CVD growth can change SWNTs from isolated ones into bundles. A new growth mechanism which combines a tip and base model for SWNT growth has been tentatively proposed. It is suggested that the small size catalytic particles prepared by pulsed arc evaporation have a potential advantage for small diameter SWNT growth. PACS 78.67.Ch; 78.67.Bf; 78.67.-n; 81.07.De; 61.46.-w     

Magnetic characterization of FeCo nanowire arrays by first-order reversal curves

FeCo nanowire arrays have been obtained by current pulse electrodeposition into nanoporous alumina templates. First-order reversal curve (FORC) diagrams have been used to investigate magnetostatic interaction and average coercivity of individual FeCo nanowires embedded in porous alumina templates. The FeCo nanowires with a wires length up to 3 μm and wires diameter ranging from 25 to 50 nm showed interacting single-domain behavior. Using FORC diagrams, the spread of coercivity distribution was seen to be almost independent of the wires diameter, but with increase in diameter the inter-wire magnetostatic interaction was increased. It was found that for arrays with higher diameter, the coercivity of the arrays is lower than the average coercivity of the individual wires. It was detected that an increase in wire diameter results in a considerable increase in the spread of the distribution in the H_u direction of FORC distribution. Curve fitting on the experimental data proved a relatively linear relation between interaction field and square diameter of the nanowires.     

温控电弧放电法大量制备单壁碳纳米管

采用可以控制真空室温度的改进型直流电弧炉，在氮气和氦气(1∶1)混合气氛下，使用Co-Ni(1∶1wt%)合金催化剂，通过控制温度等工艺条件，在容器内壁生成了大量单壁碳纳米管，尤其在阴极与阳极之间有大量的宏观网状薄膜.通过两步纯化方法：在500℃空气中烘烧30min；再用37%盐酸浸泡72h，用去离子水过滤至中性烘干.经SEM，HRTEM，XRD，Raman观察分析，纯化后其纯度高(>95％)、管径均匀(1.24—1.38nm).实验结果表明：温度强烈影响单壁碳纳米管的产量，不同温度下管子的纯度、产量都有差异，在温度为600℃时，其纯度达到70％，产量为12g/h. 关键词： 单壁碳纳米管 电弧法 温度影响     

Electrochemical functionalisation of SWNTs with poly(3,4‐ethylenedioxythiophene) evidenced by anti‐Stokes/Stokes Raman spectroscopy

The capability of anti‐Stokes/Stokes Raman spectroscopy to evaluate chemical interactions at the interface of a conducting polymer/carbon nanotubes is demonstrated. Electrochemical polymerisation of the monomer 3,4‐ethylenedioxythiophene (EDOT) on a Au support covered with a single‐walled carbon nanotube (SWNT) film immersed in a LiClO₄/CH₃CN solution was carried out. At the resonant optical excitation, which occurs when the energy of the exciting light coincides with the energy of an electronic transition, poly(3,4‐ethylenedioxythiophene) (PEDOT) deposited electrochemically as a thin film of nanometric thickness on a rough Au support presents an abnormally intense anti‐Stokes Raman spectrum. The additional increase in Raman intensity in the anti‐Stokes branch observed when PEDOT is deposited on SWNTs is interpreted as resulting from the excitation of plasmons in the metallic nanotubes. A covalent functionalisation of SWNTs with PEDOT both in un‐doped and doped states takes place when the electropolymerisation of EDOT, with stopping at +1.6 V versus Ag/Ag⁺, is performed on a SWNT film deposited on a Au plate. The presence of PEDOT covalently functionalised SWNTs is rationalised by (1) a downshift by a few wavenumbers of the polymer Raman line associated with the symmetric C C stretching mode and (2) an upshift of the radial breathing modes of SWNTs, both variations revealing an interaction between SWNTs and the conjugated polymer. Raman studies performed at different excitation wavelengths indicate that the resonant optical excitation is the key condition to observe the abnormal anti‐Stokes Raman effect. Copyright © 2010 John Wiley & Sons, Ltd.     

The effects of thermal annealing on the structure and the electrical transport properties of ultrathin gadolinia-doped ceria films grown by pulsed laser deposition

Ultrathin crystalline films of 10 mol% gadolinia-doped ceria (CGO10) are grown on MgO (100) substrates by pulsed laser deposition at a moderate temperature of 400°C. As-deposited CGO10 layers of approximately 4 nm, 14 nm, and 22 nm thickness consist of fine grains with dimensions ≤∼11 nm. The films show high density within the thickness probed in the X-ray reflectivity experiments. Thermally activated grain growth, density decrease, and film surface roughening, which may result in the formation of incoherent CGO10 islands by dewetting below a critical film thickness, are observed upon heat treatment at 400°C and 800°C. The effect of the grain coarsening on the electrical characteristics of the layers is investigated and discussed in the context of a variation of the number density of grain boundaries. The results are evaluated with regard to the use of ultrathin CGO10 films as seeding templates for the moderate temperature growth of thick solid electrolyte films with improved oxygen transport properties.     

Atomic layer deposition of HfO2: Effect of structure development on growth rate, morphology and optical properties of thin films

HfO₂ films were grown by atomic layer deposition from HfCl₄ and H₂O on Si(1 0 0), Si(1 1 1) and amorphous SiO₂ substrates at 180-750 °C and the effect of deposition temperature and film thickness on the growth rate and optical properties of the film material was studied. Crystallization, texture development and surface roughening were demonstrated to result in a noticeable growth rate increase with increasing film thickness. Highest surface roughness values were determined for the films deposited at 350-450 °C on all substrates used. The density of the film material increased with the concentration of crystalline phase but, within experimental uncertainty, was independent of orientation and sizes of crystallites in polycrystalline films. Refractive index increased with the material density. In addition, the refractive index values that were calculated from the transmission spectra depended on the surface roughness and crystallite sizes because the light scattering, which directly influenced the extinction coefficient, caused also a decrease of the refractive index determined in this way.     

Crystallographically-oriented single-crystalline copper nanowire arrays electrochemically grown into nanoporous anodic alumina templates

Highly crystallographically-oriented single-crystalline copper nanowire arrays were electrochemically deposited into nanoporous commercial alumina templates. A gold/copper backward contact was needed in the template, while the nanowires were grown from a 0.5 M CuSO₄·5H₂O solution adjusted to pH=1. The kinetics of the growing process is studied by means of current vs. time curves. The pore filling is between 80 to 90%. The structure and morphology of the wires are studied by XRD, SEM and TEM. The wires have an average diameter of 150 nm corresponding to the pore diameter of the template, with the cubic face-centered copper structure. This structure is highly oriented along the [100] direction parallel to the wire axis. The preferential growing along this direction was not previously found in the literature, which may have interesting applications when such direction is required. PACS 81.05.Bx; 82.45.Qr; 81.07.-b     

Assembly of single-walled carbon nanotubes on patterns of Au nanoparticles

We report on the assembly of single-walled carbon nanotubes (SWNTs) and gold nanoparticles (NPs) hybrid structure without any surface modification of SWNTs on patterns of Au nanoparticles (NPs). Microscale Au NP patterns were created on composite self-assembled monolayer (SAM) templates of octadecanethiol (ODT) and octanedithiol (OD) through self-assembly of Au NPs via the thiol-Au chemical bond onto the OD region. On such templates, we observed extensive adhesion and strong affinity of SWNTs on the Au NPs and no SWNT on ODT. We also examined systematically the adhesion of SWNTs on ODT with varying coverage of vapour-deposited Au. We observed little SWNT attachment even when there are high-density of Au clusters on the ODT SAM. Extensive adhesion of SWNTs is observed only when the coverage of ODT by Au is almost complete. Dynamic contact angle measurements of dichlorobenzene on the ODT/Au substrates revealed a direct correlation between the surface wettability and the SWNT assembly on a molecular template.     

Silver nanowires electrodeposited into nanoporous templates: Study of the influence of sizes on crystallinity and structural properties

In this work, results on the study of the influence of silver nanowire dimensions on the crystallinity and structural properties are presented. Silver nanowire arrays with high aspect ratios were prepared in the hollow structures of nanoporous templates using potentiostatic electrodeposition. Two types of material were employed as a template: commercial porous anodic aluminum oxide (with a mean pore diameter of 180 nm) and track-etched polycarbonate membranes (with a mean pore diameter of 15, 30 and 80 nm). Characterization of the silver nanowires has been done by EDS, XRD, TEM and electron diffraction. The degree of preferred crystallographic orientation (along the (1 1 1), (2 0 0) or (2 2 0) crystallographic planes) and the crystallite size of the silver nanowires as a function of template pore diameter are given and discussed.     

Preparation of single-walled nanotubes with the help of a Ni/Cr-based catalyst

The high-yield synthesis of single-walled carbon nanotubes (SWNTs) is carried out in an electric-arc discharge using the Ni-Cr alloy as a catalyst. A new method of introducing the catalyst into the plasma hot region is used in the synthesis. In this method, the anode with a sandwich structure consists of two longitudinal graphite rods of a rectangular cross section, between which the Ni-Cr alloy in the form of a foil having a thickness approximately equal to 0.2 mm is placed. The obtained samples are investigated using transmission electron microscopy (TEM), Raman spectroscopy, and thermogravimetry. According to the results of TEM observations, SWNTs are tied into bundles with a length of several micrometers and a diameter of about 10 nm. The Raman spectra indicate that the diameter distribution of SWNTs lies between 1.2 and 1.5 nm with a peak at approximately 1.24 nm. The SWNT content in the obtained samples is approximately 20%. Heat treatment at various temperatures with a dosed air supply leads to a noticeable mass loss of the sample and to a change in its composition. For example, thus heating to 600 K causes a mass loss of about 40%, leading to an increase in the content of SWNTs up to 35% without their noticeable destruction. Further heating above 600 K leads to a virtually complete thermal decomposition of SWNTs.     

Synthesis and characterization of nanoporous silica film via non-surfactant template sol–gel technique

Nanoporous silicon dioxide has received growing interests owing to their peculiar application potentials in conservation and storage energy. Therefore, the development of novel and simple techniques is required for raising these nanoporous materials to industrial level. In this research, we report novel strategy for the synthesis of nanoporous SiO₂ via non-surfactant template sol–gel technique for the first time. The morphology and structure of the as prepared and annealed nanoporous silica films were studied using X-ray diffraction, scanning electron microscope, Fourier transform infrared spectroscopy and nitrogen absorption/desorption technique. The results showed that highly order nanoporous silica film has been obtained at annealing temperature 600 °C with average diameter 5.1 nm and average pore volume 3.6 cm³ g⁻¹.     

Growth of AlN nanostructures by a rapid thermal process

Aluminum nitride nanorods were grown during rapid thermal annealing of multi-layered Al₂S₃ /BaS thin films. Depending on the thickness ratio between the BaS and Al₂S₃ layers, nanowires or straight nanorods were obtained. Typical dimensions for the nanorods were a diameter in the range of 50-100 nm and a length of 2-5 μm. The nanostructures are formed upon annealing at a relatively low temperature of 900 ^°C when aluminum evaporates from the thin film, but remains trapped between the thin film surface and the Si wafer, which is used as a support during the annealing. The nitrogen is provided by N₂ gas flushed through the annealing chamber. High-resolution transmission electron microscopy showed crystalline, wurtzite-structured AlN nanorods. The growth mechanism in terms of thin film composition, annealing parameters and the role of catalysts is discussed.