Tubular graphite cones with single-crystal nanotips and their antioxygenic properties.

Tubular graphite cones (TGCs) with a single-crystal nanotip have been achieved by means of microwave plasma-assisted chemical vapor deposition using in-situ-evaporated Fe catalysts. The absence of the disorder-induced D band in Raman spectra revealed the single-crystalline feature of the nanotip. TGCs were found to stem from Fe catalytic carbon spherules on the order of 100 mum diameter, whose critical role in promoting both nucleation and plasma annealing in the formation of highly crystalline TGCs is discussed. The crystalline quality of such TGCs can be further verified by the investigation of their oxidative stability in air. All TGCs can survive up to 600 degrees C without any structural variations, and a few TGCs still survive with an anisotropic etched and stepped nanotip at temperatures up to 800 degrees C, much better than CNTs. Thus, TGCs with single crystalline nanotips are potential candidates for scanning probes in high-temperature oxygen-containing environments.

Viscous state effect on the activity of Fe nanocatalysts.

Many applications of nanotubes and nanowires require controlled bottom-up engineering of these nanostructures. In catalytic chemical vapor deposition, the thermo-kinetic state of the nanocatalysts near the melting point is one of the factors ruling the morphology of the grown structures. We present theoretical and experimental evidence of a viscous state for nanoparticles near their melting point. The state exists over a temperature range scaling inversely with the catalyst size, resulting in enhanced self-diffusion and fluidity across the solid-liquid transformation. The overall effect of this phenomenon on the growth of nanotubes is that, for a given temperature, smaller nanoparticles have a larger reaction rate than larger catalysts.

Vertically aligned carbon nanotubes growth using self-assembled Ni nanoparticles produced by ion implantation

An alternative method for seeding catalyst nanoparticles for carbon nanotubes and nanowires growth is presented. Ni nanoparticles are formed inside a 450 nm SiO2 film on (100) Si wafers through the implantation of Ni ions at fluences of 7.5×1015 and 1.7×1016 ions.cm-2 and post-annealing treatments at 700, 900 and 1100°C. After exposed to the surface by HF dip etching, the Ni nanoparticles are used as catalyst for the growth of vertically aligned carbon nanotubes by direct current plasma enhanced chemical vapor deposition. © 2007 Materials Research Society.

Hafnia nanoparticles - a model system for graphene growth on a dielectric

We study graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition using optical microscopy, high resolution transmission electron microscopy and Raman spectroscopy. We find that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence we regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. HfO2 nanoparticles coated with few layer graphene by atmospheric pressure CVD with methane and hydrogen at 950 °C. (© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) Graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition (CVD) is studied. It is found that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence the authors of this Letter regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High mobility N-channel and P-channel nanocrystalline silicon thin-film transistors

We report high hole and electron mobilities in nanocrystalline silicon (nc-Si:H) top-gate staggered thin-film transistors (TFTs) fabricated by direct plasma-enhanced chemical vapor deposition (PECVD) at 260°C. The n-channel nc-Si:H TFT with n+ nc-Si:H ohmic contacts shows a field-effect electron mobility (μnFE) of 130 cm2/Vs, which increases to 150 cm2/Vs with Cr-silicide contacts, along with a field-effect hole mobility (μhFE) of 25 cm2/Vs. To the best of our knowledge, the hole and electron mobilities reported here are the highest achieved to date using direct PECVD. © 2005 IEEE.

ZnO-Based FBAR resonators with carbon nanotube electrodes

Film bulk acoustic resonator (FBAR) devices with carbon nanotube (CNT) electrodes directly grown on a ZnO film by thermal chemical vapor deposition have been fabricated. CNT electrodes possess a very low density and high acoustic impedance, which reduces the intrinsic mass loading effect resulting from the electrodes' weight and better confines the longitudinal acoustic standing waves inside the resonator, in turn providing a resonator with a higher quality factor. The influence of the CNTs on the frequency response of the FBAR devices was studied by comparing two identical sets of devices; one set comprised FBARs fabricated with chromium/ gold bilayer electrodes, and the second set comprised FBARs fabricated with CNT electrodes. It was found that the CNTs had a significant effect on attenuating traveling waves at the surface of the FBARs' membranes because of their high elastic stiffness. Three-dimensional finite element analysis of the devices fabricated was carried out, and the numerical simulations were consistent with the experimental results obtained. © 2011 IEEE.

Hot electron field emission via individually transistor-ballasted carbon nanotube arrays.

We present electronically controlled field emission characteristics of arrays of individually ballasted carbon nanotubes synthesized by plasma-enhanced chemical vapor deposition on silicon-on-insulator substrates. By adjusting the source-drain potential we have demonstrated the ability to controllable limit the emission current density by more than 1 order of magnitude. Dynamic control over both the turn-on electric field and field enhancement factor have been noted. A hot electron model is presented. The ballasted nanotubes are populated with hot electrons due to the highly crystalline Si channel and the high local electric field at the nanotube base. This positively shifts the Fermi level and results in a broad energy distribution about this mean, compared to the narrow spread, lower energy thermalized electron population in standard metallic emitters. The proposed vertically aligned carbon nanotube field-emitting electron source offers a viable platform for X-ray emitters and displays applications that require accurate and highly stable control over the emission characteristics.

Field emission properties of single-walled carbon nanotubes with a variety of emitter morphologies

Field emission properties of single-walled carbon nanotubes (SWCNTs), which were prepared through alcohol catalytic chemical vapor deposition for 10-60s, were characterized in a diode configuration. Protrusive bundles at the top surface of samples act selectively as emission sites. The number of emission sites was controlled by emitter morphologies combined with texturing of Si substrates. SWCNTs grown on a textured Si substrate exhibited a turn-on field as low as 2.4 V/μm at a field emission current density of 1 μA/cm 2. Uniform spatial luminescence (0.5 cm2) from the rear surface of the anode was revealed for SWCNTs prepared on the textured Si substrate. Deterioration of field emission properties through repetitive measurements was reduced for the textured samples in comparison with vertically aligned SWCNTs and a random network of SWCNTs prepared on flat Si substrates. Emitter morphology resulting in improved field emission properties is a crucial factor for the fabrication of SWCNT-electron sources. Morphologically controlled SWCNTs with promising emitter performance are expected to be practical electron sources. © 2008 The Japan Society of Applied Physics.

Tailoring the morphology of carbon nanotube assemblies using microgradients in the catalyst thickness

In addition to the structural control of individual carbon nanotubes (CNTs), the morphological control of their assemblies is crucial to realize miniaturized CNT devices. Microgradients in the thickness of catalyst are used to enrich the variety of available self-organized morphologies of CNTs. Microtrenches were fabricated in gate/spacer/cathode trilayers using a conventional self-aligned top-down process and catalyst exhibiting a microgradient in its thickness was formed on the cathode by sputter deposition through gate slits. CNTs, including single-walled CNTs, of up to 1μm in length were grown within 5-15 s by chemical vapor deposition. The tendency of thin CNTs to aggregate caused interactions between CNTs with different growth rates, yielding various morphologies dependent on the thickness of the catalyst. The field emission properties of several types of CNT assemblies were evaluated. The ability to produce CNTs with tailored morphologies by engineering the spatial distribution of catalysts will enhance their performance in devices. © 2011 The Japan Society of Applied Physics.

Angular distribution of field emitted electrons from vertically aligned carbon nanotube arrays

Angular field emission (FE) properties of vertically aligned carbon nanotube arrays have been measured on samples grown by plasma enhanced chemical vapor deposition and characterized by scanning electron microscope and I-V measurements. These properties determine the angular divergence of electron beams, a crucial parameter in order to obtain high brilliance FE based cathodes. From angular distributions of the electron beam transmitted through extraction grids of different mesh size and by using ray-tracing simulations, the maximum emission angle from carbon nanotube tips has been determined to be about ± 30 around the tube main axis. © 2012 American Institute of Physics.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Light absorption and electrical transport in Si:O alloys for photovoltaics

Thin films (100-500 nm) of the Si:O alloy have been systematically characterized in the optical absorption and electrical transport behavior, by varying the Si content from 43 up to 100 at. %. Magnetron sputtering or plasma enhanced chemical vapor deposition have been used for the Si:O alloy deposition, followed by annealing up to 1250 °C. Boron implantation (30 keV, 3-30× 1014 B/cm2) on selected samples was performed to vary the electrical sheet resistance measured by the four-point collinear probe method. Transmittance and reflectance spectra have been extracted and combined to estimate the absorption spectra and the optical band gap, by means of the Tauc analysis. Raman spectroscopy was also employed to follow the amorphous-crystalline (a-c) transition of the Si domains contained in the Si:O films. The optical absorption and the electrical transport of Si:O films can be continuously and independently modulated by acting on different parameters. The light absorption increases (by one decade) with the Si content in the 43-100 at. % range, determining an optical band gap which can be continuously modulated into the 2.6-1.6 eV range, respectively. The a-c phase transition in Si:O films, causing a significant reduction in the absorption coefficient, occurs at increasing temperatures (from 600 to 1100 °C) as the Si content decreases. The electrical resistivity of Si:O films can be varied among five decades, being essentially dominated by the number of Si grains and by the doping. Si:O alloys with Si content in the 60-90 at. % range (named oxygen rich silicon films), are proved to join an appealing optical gap with a viable conductivity, being a good candidate for increasing the conversion efficiency of thin-film photovoltaic cell. © 2010 American Institute of Physics.

Influence of the matrix properties on the performances of Er-doped Si nanoclusters light emitting devices

We investigated the properties of light emitting devices whose active layer consists of Er-doped Si nanoclusters (nc) generated by thermal annealing of Er-doped SiOx layers prepared by magnetron cosputtering. Differently from a widely used technique such as plasma enhanced chemical vapor deposition, sputtering allows to synthesize Er-doped Si nc embedded in an almost stoichiometric oxide matrix, so as to deeply influence the electroluminescence properties of the devices. Relevant results include the need for an unexpected low Si excess for optimizing the device efficiency and, above all, the strong reduction of the influence of Auger de-excitation, which represents the main nonradiative path which limits the performances of such devices and their application in silicon nanophotonics. © 2010 American Institute of Physics.

Light absorption in silicon quantum dots embedded in silica

The photon absorption in Si quantum dots (QDs) embedded in SiO2 has been systematically investigated by varying several parameters of the QD synthesis. Plasma-enhanced chemical vapor deposition (PECVD) or magnetron cosputtering (MS) have been used to deposit, upon quartz substrates, single layer, or multilayer structures of Si-rich- SiO2 (SRO) with different Si content (43-46 at. %). SRO samples have been annealed for 1 h in the 450-1250 °C range and characterized by optical absorption measurements, photoluminescence analysis, Rutherford backscattering spectrometry and x-ray Photoelectron Spectroscopy. After annealing up to 900 °C SRO films grown by MS show a higher absorption coefficient and a lower optical bandgap (∼2.0 eV) in comparison with that of PECVD samples, due to the lower density of Si-Si bonds and to the presence of nitrogen in PECVD materials. By increasing the Si content a reduction in the optical bandgap has been recorded, pointing out the role of Si-Si bonds density in the absorption process in small amorphous Si QDs. Both the photon absorption probability and energy threshold in amorphous Si QDs are higher than in bulk amorphous Si, evidencing a quantum confinement effect. For temperatures higher than 900 °C both the materials show an increase in the optical bandgap due to the amorphous-crystalline transition of the Si QDs. Fixed the SRO stoichiometry, no difference in the optical bandgap trend of multilayer or single layer structures is evidenced. These data can be profitably used to better implement Si QDs for future PV technologies. © 2009 American Institute of Physics.

Microstructural evolution of SiOx films and its effect on the luminescence of Si nanoclusters

In this paper we demonstrate that the structural and optical properties of Si nanoclusters (Si ncs) formed by thermal annealing of SiOx films prepared by plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering are very different. In fact, at a fixed Si excess and annealing temperature, photoluminescence (PL) spectra of sputtered samples are redshifted with respect to PECVD samples, denoting a larger Si ncs size. In addition, PL intensity reaches a maximum in sputtered films at annealing temperatures much lower than those needed in PECVD films. These data are correlated with structural properties obtained by energy filtered transmission electron microscopy and electron energy loss spectroscopy. It is shown that in PECVD films only around 30% of the Si excess agglomerates in clusters while an almost complete agglomeration occurs in sputtered films. These data are explained on the basis of the different initial structural properties of the as-deposited films that become crucial for the subsequent evolution. © 2008 American Institute of Physics.