Chemical vapor deposition of nanocrystalline graphene directly on arbitrary high-temperature insulating substrates

Large area uniform nanocrystalline graphene is grown by chemical vapor deposition on arbitrary insulating substrates that can survive ∼1000°C. The as-synthesized graphene is nanocrystalline with a domain size in the order of ∼10 nm. The material possesses a transparency and conductivity similar to standard graphene fabricated by exfoliation or catalysis. A noncatalytic mechanism is proposed to explain the experimental phenomena. The developed technique is scalable and reproducible, compatible with the existing semiconductor technology, and thus can be very useful in nanoelectronic applications such as transparent electronics, nanoelectromechanical systems, as well as molecular electronics. © 2012 IEEE.

The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

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.

Electrical transport and percolation in magnetoresistive manganite / insulating oxide composites: case of La0.7Ca0.3MnO3 / Mn3O4

We report the results of electrical resistivity measurements carried out on well-sintered La0.7Ca0.3MnO3 / Mn3O4 composite samples with almost constant composition of the magnetoresistive manganite phase (La0.7Ca0.3MnO3). A percolation threshold (fc) occurs when the La0.7Ca0.3MnO3 volume fraction is ~ 0.19. The dependence of the electrical resistivity as a function of La0.7Ca0.3MnO3 volume fraction (fLCMO) can be described by percolation-like phenomenological equations. Fitting the conducting regime (fLCMO > fc) by the percolation power law returns a critical exponent t value of 2.0 +/- 0.2 at room temperature and 2.6 +/-0.2 at 5 K. The increase of t is ascribed to the influence of the grain boundaries on the electrical conduction process at low temperature.

La 0.7Ca 0.3MnO 3 / Mn 3O 4 composites: Does an insulating secondary phase always enhance the low field magnetoresistance of manganites

Composites of magnetoresistive La 0.7Ca 0.3MnO 3 (LCMO) with insulating Mn 3O 4 are useful as a model system because no foreign cation is introduced in the LCMO phase by interdiffusion during the heat treatment. Here we report the magnetotransport properties as a function of sintering temperature T sinter for a fixed LCMO/Mn 3O 4 ratio. Decreasing T sinter from 1250 °C to 800 °C causes an increase in low field magnetoresistance (LFMR) that correlates with the decrease in crystallite size (CS) of the LCMO phase. When plotting LFMR at (77 K, 0.5 T) versus 1/CS, we find that the data for the LCMO/Mn 3O 4 composites sintered between 800 °C and 1250 °C follow the same trend line as data from the literature for pure LCMO samples with crystallite size >∼25 nm. This differs from the LFMR enhancement observed by many authors in the usual manganite composites, i.e., composites where the insulating phase contains cations other than La, Ca or Mn. This difference suggests that diffusion of foreign cations into the grain boundary region is a necessary ingredient for the enhanced LFMR. © 2012 American Institute of Physics.

Mechanics of capillary forming of aligned carbon nanotube assemblies.

Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called "capillary forming") of carbon nanotube (CNT) microstructures, combining in situ optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor-liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials.

Capillary bending of Janus carbon nanotube micropillars.

We present a scalable process for the fabrication of slanted carbon nanotube micropillar arrays by inclined metal deposition and capillary self-assembly. Local control of the micropillar angle from vertical to nearly horizontal is achieved, and is explained using a finite element model. These structures may be useful for microscale contacts and anisotropic smart surfaces.

Structurally programmed capillary folding of carbon nanotube assemblies.

We demonstrate the fabrication of horizontally aligned carbon nanotube (HA-CNT) networks by spatially programmable folding, which is induced by self-directed liquid infiltration of vertical CNTs. Folding is caused by a capillary buckling instability and is predicted by the elastocapillary buckling height, which scales with the wall thickness as t(3/2). The folding direction is controlled by incorporating folding initiators at the ends of the CNT walls, and the initiators cause a tilt during densification which precedes buckling. By patterning these initiators and specifying the wall geometry, we control the dimensions of HA-CNT patches over 2 orders of magnitude and realize multilayered and multidirectional assemblies. Multidirectional HA-CNT patterns are building blocks for custom design of nanotextured surfaces and flexible circuits.

Diverse 3D microarchitectures made by capillary forming of carbon nanotubes.

A new technology called capillary forming enables transformation of vertically aligned nanoscale filaments into complex three-dimensional microarchitectures. We demonstrate capillary forming of carbon nanotubes into diverse forms having intricate bends, twists, and multidirectional textures. In addition to their novel geometries, these structures have mechanical stiffness exceeding that of microfabrication polymers, and can be used as masters for replica molding

Fast response CO2 sensor for automotive exhaust gas analysis

A fast response sensor for measuring carbon dioxide concentration has been developed for laboratory research and tested on a spark ignition engine. The sensor uses the well known infra-red absorption technique with a miniaturized detection system and short capillary sampling tubes, giving a time constant of approximately 5 milliseconds; this is sufficiently fast to observe changes in CO2 levels on a cycle-by-cycle basis under normal operating conditions. The sensor is easily located in the exhaust system and operates continuously. The sensor was tested on a standard production four cylinder spark-ignition engine to observe changes in CO2 concentration in exhaust gas under steady state and transient operating conditions. The processed sensor signal was compared to a standard air-to-fuel ratio (AFR) sensor in the exhaust stream and the results are presented here. The high frequency response CO2 measurements give new insights into both engine and catalyst transient operation. Copyright © 1999 Society of Automotive Engineers, Inc.

Thermogravimetric study on the hydration of reactive magnesia and silica mixture at room temperature

The synthesis of magnesium silicate hydrate (MSH), which has wide applications in both construction and environmental fields, has been studied for decades. However, it is known that the characteristics of magnesia (MgO) vary significantly depending on their calcination conditions, which is expected to affect their performance in the MgO-SiO2-H2O system. This paper investigated the effect of different MgO and silica sources on the formation of magnesium silicate hydrate (MSH) at room temperature. The hydration process was studied by mixing commercial reactive MgO and silica powders with water and curing for 1, 7 and 28 days. The hydration products were analysed with the help of X-ray diffraction (XRD) and thermogravimatric analysis (TGA). The results showed the continuous consumption of MgO and the existence of MSH and brucite and other minor phases such as magnesite and calcite. It is found that the Mg and Si sources have significant effect on the hydration process of MgO-SiO2-H2O system. The reaction degree is controlled by the availability of dissolved Mg and Si in the solution. The former is determined by the reactivity of MgO and the latter is related to the reactivity of the silica as well as the pH of the system. © 2013 Elsevier B.V. All rights reserved.

The predicted compressive strength of a pyramidal lattice made from case hardened steel tubes

A sandwich panel with a core made from solid pyramidal struts is a promising candidate for multifunctional application such as combined structural and heat-exchange function. This study explores the performance enhancement by making use of hollow struts, and examines the elevation in the plastic buckling strength by either strain hardening or case hardening. Finite element simulations are performed to quantify these enhancements. Also, the sensitivity of competing collapse modes to tube geometry and to the depth of case hardening is determined. A comparison with other lattice materials reveals that the pyramidal lattice made from case hardened steel tubes outperforms lattices made from solid struts of aluminium or titanium and has a comparable strength to a core made from carbon fibre reinforced polymers. © 2013 Elsevier Ltd. All rights reserved.

Towards more sustainable and environmentally-friendly concretes: The use of silica fume

Concrete is the most widely used construction material. At the same time, however, the concrete industry is a major CO2 emitter thus contributing towards global warming. While enhanced efficiency in the production of concrete is not likely to dramatically reduce the CO2 emissions, cement replacement by a supplementary material or mineral additive, such as silica fume, which is not associated with CO2 emission, can substantially reduce the aforementioned problem. The present work discusses the benefits of incorporating mineral additives in concrete and shows that these additives can improve both the mechanical and physical properties of the end-product, and hence its durability, albeit with a reduction in cement content. © 2009 WIT Press.

Calculation of metallic and insulating phases of V2O3 by hybrid density functionals.

The electronic structure of vanadium sesquioxide V2O3 in its different phases has been calculated using the screened exchange hybrid density functional. The hybrid functional accurately reproduces the experimental electronic properties of all three phases, the paramagnetic metal (PM) phase, the anti-ferromagnetic insulating phase, and the Cr-doped paramagnetic insulating (PI) phase. We find that a fully relaxed supercell model of the Cr-doped PI phase based on the corundum structure has a monoclinic-like local strain around the substitutional Cr atoms. This is found to drive the PI-PM transition, consistent with a Peierls-Mott transition. The PI phase has a calculated band gap of 0.15 eV, in good agreement with experiment.