Increased size selectivity of Si quantum dots on SiC at low substrate temperatures : an ion-assisted self-organization approach

A simple, effective, and innovative approach based on ion-assisted self-organization is proposed to synthesize size-selected Si quantum dots (QDs) on SiC substrates at low substrate temperatures. Using hybrid numerical simulations, the formation of Si QDs through a self-organization approach is investigated by taking into account two distinct cases of Si QD formation using the ionization energy approximation theory, which considers ionized in-fluxes containing Si3+ and Si1+ ions in the presence of a microscopic nonuniform electric field induced by a variable surface bias. The results show that the highest percentage of the surface coverage by 1 and 2 nm size-selected QDs was achieved using a bias of -20 V and ions in the lowest charge state, namely, Si1+ ions in a low substrate temperature range (227-327 °C). As low substrate temperatures (≤500 °C) are desirable from a technological point of view, because (i) low-temperature deposition techniques are compatible with current thin-film Si-based solar cell fabrication and (ii) high processing temperatures can frequently cause damage to other components in electronic devices and destroy the tandem structure of Si QD-based third-generation solar cells, our results are highly relevant to the development of the third-generation all-Si tandem photovoltaic solar cells.

Silicon on silicon : self-organized nanotip arrays formed in reactive Ar+H2 plasmas

The formation of arrays of vertically aligned nanotips on a moderately heated (up to 500 degrees C) Si surface exposed to reactive low-temperature radio frequency (RF) Ar+H(2) plasmas is studied. It is demonstrated that the nanotip surface density, aspect ratio and height dispersion strongly depend on the substrate temperature, discharge power, and gas composition. It is shown that nanotips with aspect ratios from 2.0 to 4.0 can only be produced at a higher RF power density (41.7 mW cm(-3)) and a hydrogen content of about 60%, and that larger aspect ratios can be achieved at substrate temperatures of about 300 degrees C. The use of higher (up to 500 degrees C) temperatures leads to a decrease of the aspect ratio but promotes the formation of more uniform arrays with the height dispersion decreasing to 1.5. At lower (approximately 20 mW cm(-3)) RF power density, only semispherical nanodots can be produced. Based on these experimental results, a nanotip formation scenario is proposed suggesting that sputtering, etching, hydrogen termination, and atom/radical re-deposition are the main concurrent mechanisms for the nanostructure formation. Numerical calculations of the ion flux distribution and hydrogen termination profiles can be used to predict the nanotip shapes and are in a good agreement with the experimental results. This approach can be applied to describe the kinetics of low-temperature formation of other nanoscale materials by plasma treatment.

Temperature-dependent properties of nc-Si thin films synthesized in low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas

Silicon thin films were synthesized simultaneously on single-crystal silicon and glass substrates by lowpressure, thermally nonequilibrium, high-density inductively coupled plasma-assisted chemical vapor deposition from the silane precursor gas without any additional hydrogen dilution in a broad range of substrate temperatures from 100 to 500 °C. The effect of the substrate temperature on the morphological, structural and optical properties of the synthesized silicon thin films is systematically studied by X-ray diffractometry, Raman spectroscopy, UV-vis spectroscopy, and scanning electron microscopy. It is shown that the formation of nanocrystalline silicon (nc-Si) occurs when the substrate temperature is higher than 200 °C and that all the deposited nc-Si films have a preferential growth along the (111) direction. However, the mean grain size of the (111) orientation slightly and gradually decreases while the mean grain size of the (220) orientation shows a monotonous increase with the increased substrate temperature from 200 to 500 °C. It is also found that the crystal volume fraction of the synthesized nc-Si thin films has a maximum value of ∼69.1% at a substrate temperature of 300 rather than 500 °C. This rather unexpected result is interpreted through the interplay of thermokinetic surface diffusion and hydrogen termination effects. Furthermore, we have also shown that with the increased substrate temperature from 100 to 500 °C, the optical bandgap is reduced while the growth rates tend to increase. The maximum rates of change of the optical bandgap and the growth rates occur when the substrate temperature is increased from 400 to 500 °C. These results are highly relevant to the development of photovoltaic thin-film solar cells, thin-film transistors, and flat-panel displays.

Effects of ions and atomic hydrogen in plasma-assisted growth of single-walled carbon nanotubes

The growth of single-walled carbon nanotubes (SWCNTs) in plasma-enhanced chemical vapor deposition (PECVD) is studied using a surface diffusion model. It is shown that at low substrate temperatures (≤1000 K), the atomic hydrogen and ion fluxes from the plasma can strongly affect nanotube growth. The ion-induced hydrocarbon dissociation can be the main process that supplies carbon atoms for SWCNT growth and is responsible for the frequently reported higher (compared to thermal chemical vapor deposition) nanotube growth rates in plasma-based processes. On the other hand, excessive deposition of plasma ions and atomic hydrogen can reduce the diffusion length of the carbon-bearing species and their residence time on the nanotube lateral surfaces. This reduction can adversely affect the nanotube growth rates. The results here are in good agreement with the available experimental data and can be used for optimizing SWCNT growth in PECVD.

Customizing electron confinement in plasma-assembled Si/AlN nanodots for solar cell applications

Size-uniform Si nanodots (NDs) are synthesized on an AlN buffer layer at low Si(111) substrate temperatures using inductively coupled plasma-assisted magnetron sputtering deposition. High-resolution electron microscopy reveals that the sizes of the Si NDs range from 9 to 30 nm. Room-temperature photoluminescence (PL) spectra indicate that the energy peak shifts from 738 to 778 nm with increasing the ND size. In this system, the quantum confinement effect is fairly strong even for relatively large (up to 25 nm in diameter) NDs, which is promising for the development of the next-generation all-Si tandem solar cells capable of effectively capturing sunlight photons with the energies between 1.7 (infrared: large NDs) and 3.4 eV (ultraviolet: small NDs). The strength of the resulting electron confinement in the Si/AlN ND system is evaluated and justified by analyzing the measured PL spectra using the ionization energy theory approximation.

Plasma heating effects in catalyzed growth of carbon nanofibres

A theoretical model describing the plasma-assisted growth of carbon nanofibres (CNFs) that accounts for the nanostructure heating by ion and etching gas fluxes from the plasma is developed. Using the model, it is shown that fluxes from the plasma environment can substantially increase the temperature of the catalyst nanoparticle located on the top of the CNF with respect to the substrate temperature. The difference between the catalyst and the substrate temperatures depends on the substrate width, the length of the CNF, the neutral gas density and temperature as well as the densities of the ions and atoms of the etching gas. In addition to the heating of the nanostructure, the ions and etching gas atoms from the ionized gas environment also strongly affect the CNF growth rates. Due to ion bombardment, the CNF growth rates in plasma enhanced chemical vapour deposition may be much higher than the rates in similar neutral gas-based thermal processes. The CNF growth model, which accounts for the nanostructure heating by the plasma-generated species, provides the growth rates that are in better agreement with the available experimental data on CNF growth than the models in which the heating effects are ignored.

Self-assembly of uniform carbon nanotip structures in chemically active inductively coupled plasmas

Self-assembly of carbon nanotip (CNTP) structures on Ni-based catalyst in chemically active inductively coupled plasmas of CH 4 + H 2 + Ar gas mixtures is reported. By varying the process conditions, it appears possible to control the shape, size, and density of CNTPs, content of the nanocrystalline phase in the films, as well as to achieve excellent crystallinity, graphitization, uniformity and vertical alignment of the resulting nanostructures at substrate temperatures 300-500°C and low gas pressures (below 13.2 Pa). This study provides a simple and efficient plasma-enhanced chemical vapor deposition (PECVD) technique for the fabrication of vertically aligned CNTP arrays for electron field emitters.

Indium clusters on the Ge (5× 5) wetting layer of Si (111)- 7× 7

The adsorption of In on the Si(111)−Ge(5×5) surface reconstruction has been studied with scanning tunneling microscopy and ab initio calculations to investigate the possibility of using this reconstruction as a template for cluster formation. As with In adsorption on Si(111)−7×7 at low substrate temperatures and low In fluences, the In adatoms are found to preferentially adsorb on the faulted half-unit cell. However, in contrast to In adsorption on Si(111)−7×7, the In adatoms are also frequently found in the unfaulted half-unit cell at low coverages. The filling of unfaulted unit cell halves is primarily due to the formation of large clusters that span multiple substrate half-unit cells. Moreover, many of the faulted half-unit cells have a streaked appearance that indicates that surface atoms within them are mobile.

Patterns of substrate utilization during long-term incubations at different temperatures

Microorganisms play key roles in biogeochemical cycling by facilitating the release of nutrients from organic compounds. In doing so, microbial communities use different organic substrates that yield different amounts of energy for maintenance and growth of the community. Carbon utilization efficiency (CUE) is a measure of the efficiency with which substrate carbon is metabolized versus mineralized by the microbial biomass. In the face of global change, we wanted to know how temperature affected the efficiency by which the soil microbial community utilized an added labile substrate, and to determine the effect of labile soil carbon depletion (through increasing duration of incubation) on the community's ability to respond to an added substrate. Cellobiose was added to soil samples as a model compound at several times over the course of a long-term incubation experiment to measure the amount of carbon assimilated or lost as CO2 respiration. Results indicated that in all cases, the time required for the microbial community to take up the added substrate increased as incubation time prior to substrate addition increased. However, the CUE was not affected by incubation time. Increased temperature generally decreased CUE, thus the microbial community was more efficient at 15 degrees C than at 25 degrees C. These results indicate that at warmer temperatures microbial communities may release more CO2 per unit of assimilated carbon. Current climate-carbon models have a fixed CUE to predict how much CO2 will be released as soil organic matter is decomposed. Based on our findings, this assumption may be incorrect due to variation of CUE with changing temperature. (c) 2008 Elsevier Ltd. All rights reserved.

Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles

Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald–Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.