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.

Non-destructive characterization of structural hierarchy within aligned carbon nanotube assemblies

Understanding and controlling the hierarchical self-assembly of carbon nanotubes (CNTs) is vital for designing materials such as transparent conductors, chemical sensors, high-performance composites, and microelectronic interconnects. In particular, many applications require high-density CNT assemblies that cannot currently be made directly by low-density CNT growth, and therefore require post-processing by methods such as elastocapillary densification. We characterize the hierarchical structure of pristine and densified vertically aligned multi-wall CNT forests, by combining small-angle and ultra-small-angle x-ray scattering (USAXS) techniques. This enables the nondestructive measurement of both the individual CNT diameter and CNT bundle diameter within CNT forests, which are otherwise quantified only by delicate and often destructive microscopy techniques. Our measurements show that multi-wall CNT forests grown by chemical vapor deposition consist of isolated and bundled CNTs, with an average bundle diameter of 16 nm. After capillary densification of the CNT forest, USAXS reveals bundles with a diameter 4 m, in addition to the small bundles observed in the as-grown forests. Combining these characterization methods with new CNT processing methods could enable the engineering of macro-scale CNT assemblies that exhibit significantly improved bulk properties. © 2011 American Institute of Physics.

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.

Precursor flow rate manipulation for the controlled fabrication of twin-free GaAs nanowires on silicon substrates

Vertically oriented GaAs nanowires (NWs) are grown on Si(111) substrates using metal-organic chemical vapor deposition. Controlled epitaxial growth along the 111 direction is demonstrated following the deposition of thin GaAs buffer layers and the elimination of structural defects, such as twin defects and stacking faults, is found for high growth rates. By systematically manipulating the AsH 3 (group-V) and TMGa (group-III) precursor flow rates, it is found that the TMGa flow rate has the most significant effect on the nanowire quality. After capping the minimal tapering and twin-free GaAs NWs with an AlGaAs shell, long exciton lifetimes (over 700ps) are obtained for high TMGa flow rate samples. It is observed that the Ga adatom concentration significantly affects the growth of GaAs NWs, with a high concentration and rapid growth leading to desirable characteristics for optoelectronic nanowire device applications including improved morphology, crystal structure and optical performance. © 2012 IOP Publishing Ltd.

Taper-free and kinked germanium nanowires grown on silicon via purging and the two-temperature process

We investigate the growth procedures for achieving taper-free and kinked germanium nanowires epitaxially grown on silicon substrates by chemical vapor deposition. Singly and multiply kinked germanium nanowires consisting of 111 segments were formed by employing a reactant gas purging process. Unlike non-epitaxial kinked nanowires, a two-temperature process is necessary to maintain the taper-free nature of segments in our kinked germanium nanowires on silicon. As an application, nanobridges formed between (111) side walls of V-grooved (100) silicon substrates have been demonstrated. © 2012 IOP Publishing Ltd.

Taper-free and vertically oriented Ge nanowires on Ge/Si substrates grown by a two-temperature process

Taper-free and vertically oriented Ge nanowires were grown on Si (111) substrates by chemical vapor deposition with Au nanoparticle catalysts. To achieve vertical nanowire growth on the highly lattice mismatched Si substrate, a thin Ge buffer layer was first deposited, and to achieve taper-free nanowire growth, a two-temperature process was employed. The two-temperature process consisted of a brief initial base growth step at high temperature followed by prolonged growth at lower temperature. Taper-free and defect-free Ge nanowires grew successfully even at 270 °C, which is 90 °C lower than the bulk eutectic temperature. The yield of vertical and taper-free nanowires is over 90%, comparable to that of vertical but tapered nanowires grown by the conventional one-temperature process. This method is of practical importance and can be reliably used to develop novel nanowire-based devices on relatively cheap Si substrates. Additionally, we observed that the activation energy of Ge nanowire growth by the two-temperature process is dependent on Au nanoparticle size. The low activation energy (∼5 kcal/mol) for 30 and 50 nm diameter Au nanoparticles suggests that the decomposition of gaseous species on the catalytic Au surface is a rate-limiting step. A higher activation energy (∼14 kcal/mol) was determined for 100 nm diameter Au nanoparticles which suggests that larger Au nanoparticles are partially solidified and that growth kinetics become the rate-limiting step. © 2011 American Chemical Society.

Defect-free GaAs/AlGaAs Core-shell nanowires on Si substrates

We report straight and vertically aligned defect-free GaAs nanowires grown on Si(111) substrates by metal-organic chemical vapor deposition. By deposition of thin GaAs buffer layers on Si substrates, these nanowires could be grown on the buffer layers with much less stringent conditions as otherwise imposed by epitaxy of III-V compounds on Si. Also, crystal-defect-free GaAs nanowires were grown by using either a two-temperature growth mode consisting of a short initial nucleation step under higher temperature followed by subsequent growth under lower temperature or a rapid growth rate mode with high source flow rate. These two growth modes not only eliminated planar crystallographic defects but also significantly reduced tapering. Core-shell GaAs-AlGaAs nanowires grown by the two-temperature growth mode showed improved optical properties with strong photoluminescence and long carrier life times. © 2011 American Chemical Society.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Vertically oriented epitaxial germanium nanowires on silicon substrates using thin germanium buffer layers.

We demonstrate a method to realize vertically oriented Ge nanowires on Si(111) substrates. Ge nanowires were grown by chemical vapor deposition using Au nanoparticles to seed nanowire growth via a vapor-liquid-solid growth mechanism. Rapid oxidation of Si during Au nanoparticle application inhibits the growth of vertically oriented Ge nanowires directly on Si. The present method employs thin Ge buffer layers grown at low temperature less than 600 degrees C to circumvent the oxidation problem. By using a thin Ge buffer layer with root-mean-square roughness of approximately 2 nm, the yield of vertically oriented Ge nanowires is as high as 96.3%. This yield is comparable to that of homoepitaxial Ge nanowires. Furthermore, branched Ge nanowires could be successfully grown on these vertically oriented Ge nanowires by a secondary seeding technique. Since the buffer layers are grown under moderate conditions without any high temperature processing steps, this method has a wide process window highly suitable for Si-based microelectronics.

Evolution of Wurtzite Structured GaAs Shells Around InAs Nanowire Cores.

GaAs was radially deposited on InAs nanowires by metal-organic chemical vapor deposition and resultant nanowire heterostructures were characterized by detailed electron microscopy investigations. The GaAs shells have been grown in wurtzite structure, epitaxially on the wurtzite structured InAs nanowire cores. The fundamental reason of structural evolution in terms of material nucleation and interfacial structure is given.

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process.

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.