High-frequency conductivity of optically excited charge carriers in hydrogenated nanocrystalline silicon investigated by spectroscopic femtosecond pump-probe reflectivity measurements

We report an investigation into the high-frequency conductivity of optically excited charge carriers far from equilibrium with the lattice. The investigated samples consist of hydrogenated nanocrystalline silicon films grown on a thin film of silicon oxide on top of a silicon substrate. For the investigation, we used an optical femtosecond pump-probe setup to measure the reflectance change of a probe beam. The pump beam ranged between 580 and 820nm, whereas the probe wavelength spanned 770 to 810nm. The pump fluence was fixed at 0.6mJ/cm2. We show that at a fixed delay time of 300fs, the conductivity of the excited electron-hole plasma is described well by a classical conductivity model of a hot charge carrier gas found at Maxwell-Boltzmann distribution, while Fermi-Dirac statics is not suitable. This is corroborated by values retrieved from pump-probe reflectance measurements of the conductivity and its dependence on the excitation wavelength and carrier temperature. The conductivity decreases monotonically as a function of the excitation wavelength, as expected for a nondegenerate charge carrier gas.

Catalysing sustainable fuel and chemical synthesis

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century’s grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands.

In situ synthesis and catalytic activity in CO oxidation of metal nanoparticles supported on porous nanocrystalline silicon

Reactive surface of mesoporous nanocrystalline silicon was used to synthesise noble metal nanoparticles via in situ reduction of the precursor salt solutions. The synthetic methodology for metal nanoparticle formation was systematically developed, and reaction conditions of metal salts reduction were optimised to prepare nanoparticles of controlled size distribution in the order 5–10 nm inside the mesoporous silicon template. CO oxidation was used as a test reaction for the synthesised Pt/porous silicon catalysts. Sharp reaction light-off was observed at about 120 °C on the optimised catalysts. The catalysts were shown to be stable in the extended steady-state runs and in the catalysts re-use experiments. Metal nanoparticles were shown to be stable to sintering at elevated temperatures up to 1000 °C. However, after thermal treatment on air, Pt nanoparticles were covered by a SiOx layer and were less active in CO oxidation.

Unravelling the photodegradation mechanisms of a low bandgap polymer by combining experimental and modeling approaches

Large-scale introduction of Organic Solar Cells (OSCs) onto the market is currently limited by their poor stability in light and air, factors present in normal working conditions for these devices. Thus, great efforts have to be undertaken to understand the photodegradation mechanisms of their organic materials in order to find solutions that mitigate these effects. This study reports on the elucidation of the photodegradation mechanisms occurring in a low bandgap polymer, namely, Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]). Complementary analytical techniques (AFM, HS-SPME-GC-MS, UV-vis and IR spectroscopy) have been employed to monitor the modification of the chemical structure of the polymer upon photooxidative aging and the subsequent consequences on its architecture and nanomechanical properties. Furthermore, these different characterization techniques have been combined with a theoretical approach based on quantum chemistry to elucidate the evolution of the polymer alkyl side chains and backbone throughout exposure. Si-PCPDTBT is shown to be more stable against photooxidation than the commonly studied p-type polymers P3HT and PCDTBT, while modeling demonstrated the benefits of using silicon as a bridging atom in terms of photostability. (Figure Presented).

Modeling security and cooperation in wireless networks using game theory

This research involves the design, development, and theoretical demonstration of models resulting in integrated misbehavior resolution protocols for ad hoc networked devices. Game theory was used to analyze strategic interaction among independent devices with conflicting interests. Packet forwarding at the routing layer of autonomous ad hoc networks was investigated. Unlike existing reputation based or payment schemes, this model is based on repeated interactions. To enforce cooperation, a community enforcement mechanism was used, whereby selfish nodes that drop packets were punished not only by the victim, but also by all nodes in the network. Then, a stochastic packet forwarding game strategy was introduced. Our solution relaxed the uniform traffic demand that was pervasive in other works. To address the concerns of imperfect private monitoring in resource aware ad hoc networks, a belief-free equilibrium scheme was developed that reduces the impact of noise in cooperation. This scheme also eliminated the need to infer the private history of other nodes. Moreover, it simplified the computation of an optimal strategy. The belief-free approach reduced the node overhead and was easily tractable. Hence it made the system operation feasible. Motivated by the versatile nature of evolutionary game theory, the assumption of a rational node is relaxed, leading to the development of a framework for mitigating routing selfishness and misbehavior in Multi hop networks. This is accomplished by setting nodes to play a fixed strategy rather than independently choosing a rational strategy. A range of simulations was carried out that showed improved cooperation between selfish nodes when compared to older results. Cooperation among ad hoc nodes can also protect a network from malicious attacks. In the absence of a central trusted entity, many security mechanisms and privacy protections require cooperation among ad hoc nodes to protect a network from malicious attacks. Therefore, using game theory and evolutionary game theory, a mathematical framework has been developed that explores trust mechanisms to achieve security in the network. This framework is one of the first steps towards the synthesis of an integrated solution that demonstrates that security solely depends on the initial trust level that nodes have for each other.^

Incorporating variable peak -to -daily ratios in the equilibrium traffic assignment procedure of the Florida Standard Urban Transportation Modeling Structure (FSUTMS)

The standard highway assignment model in the Florida Standard Urban Transportation Modeling Structure (FSUTMS) is based on the equilibrium traffic assignment method. This method involves running several iterations of all-or-nothing capacity-restraint assignment with an adjustment of travel time to reflect delays encountered in the associated iteration. The iterative link time adjustment process is accomplished through the Bureau of Public Roads (BPR) volume-delay equation. Since FSUTMS' traffic assignment procedure outputs daily volumes, and the input capacities are given in hourly volumes, it is necessary to convert the hourly capacities to their daily equivalents when computing the volume-to-capacity ratios used in the BPR function. The conversion is accomplished by dividing the hourly capacity by a factor called the peak-to-daily ratio, or referred to as CONFAC in FSUTMS. The ratio is computed as the highest hourly volume of a day divided by the corresponding total daily volume. ^ While several studies have indicated that CONFAC is a decreasing function of the level of congestion, a constant value is used for each facility type in the current version of FSUTMS. This ignores the different congestion level associated with each roadway and is believed to be one of the culprits of traffic assignment errors. Traffic counts data from across the state of Florida were used to calibrate CONFACs as a function of a congestion measure using the weighted least squares method. The calibrated functions were then implemented in FSUTMS through a procedure that takes advantage of the iterative nature of FSUTMS' equilibrium assignment method. ^ The assignment results based on constant and variable CONFACs were then compared against the ground counts for three selected networks. It was found that the accuracy from the two assignments was not significantly different, that the hypothesized improvement in assignment results from the variable CONFAC model was not empirically evident. It was recognized that many other factors beyond the scope and control of this study could contribute to this finding. It was recommended that further studies focus on the use of the variable CONFAC model with recalibrated parameters for the BPR function and/or with other forms of volume-delay functions. ^

Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Annotated record and chemical composition of ferromanganese concretions and crusts sampled from the lakes and streams of Norway

The main objective of the project was to develop a geochemical method for exploration of ores associated with granitic rocks. Fe and Mn oxidates were sampled in streambeds and lakes from 129 localities in Southeastern Norway. 65 of these localities are situated in the northern Oslo Graben. The samples were examined mineralogically and chemically by a variety of methods. Geochemical maps of the element content in oxidates show regional distribution patterns for several elements. Sampling and analysis of oxidates can be used in exploration for mineralizations such as the Skrukkelia Mo-deposit in the northern Oslo Graben. New anomalies (especially for Zn and W) have been detected. Appendix I contains a description of samples, chemical and mineralogical determinations performed on the samples, backscattered electron image-, X-ray image- and scanning electron image pictures of the oxidate preparates. Appendix II contains spectral plots, point analysis with the microprobe, X-ray diffractograms, analytical results, correlation coefficient matrix, scatterplots, frequency distributions and information on data storage. Appendix III containS maps of the element content in oxidates.

Chemical composition of Late Cenozoic volcanic and volcaniclastic deposits from the western Woodlark Basin area, SW Pacific

Tephra fallout layers and volcaniclastic deposits, derived from volcanic sources around and on the Papuan Peninsula, form a substantial part of the Woodlark Basin marine sedimentary succession. Sampling by the Ocean Drilling Program Leg 180 in the western Woodlark Basin provides the opportunity to document the distribution of the volcanically-derived components as well as to evaluate their chronology, chemistry, and isotope compositions in order to gain information on the volcanic sources and original magmatic systems. Glass shards selected from 57 volcanogenic layers within the sampled Pliocene-Pleistocene sedimentary sequence show predominantly rhyolitic compositions, with subordinate basaltic andesites, basaltic trachy-andesites, andesites, trachy-andesites, dacites, and phonolites. It was possible to correlate only a few of the volcanogenic layers between sites using geochemical and age information apparently because of the formation of strongly compartmentalised sedimentary realms on this actively rifting margin. In many cases it was possible to correlate Leg 180 volcanic components with their eruption source areas based on chemical and isotope compositions. Likely sources for a considerable number of the volcanogenic deposits are Moresby and Dawson Strait volcanoes (D'Entrecasteaux Islands region) for high-K calc-alkaline glasses. The Dawson Strait volcanoes appear to represent the source for five peralkaline tephra layers. One basaltic andesitic volcaniclastic layer shows affinities to basaltic andesites from the Woodlark spreading tip and Cheshire Seamount. For other layers, a clear identification of the sources proved impossible, although their isotope and chemical signatures suggest similarities to south-west Pacific subduction volcanism, e.g. New Britain and Tonga- Kermadec island arcs. Volcanic islands in the Trobriand Arc (for example, Woodlark Island Amphlett Islands and/or Egum Atoll) are probable sources for several volcaniclastic layers with ages between 1.5 to 3 Ma. The Lusancay Islands can be excluded as a source for the volcanogenic layers found during Leg 180. Generally, the volcanogenic layers indicate much calc-alkaline rhyolitic volcanism in eastern Papua since 3.8 Ma. Starting at 135 ka, however, peralkaline tephra layers appear. This geochemical change in source characteristics might reflect the onset of a change in geotectonic regime, from crustal subduction to spreading, affecting the D'Entrecasteaux Islands region. Initial 143Nd/144Nd ratios as low as 0.5121 and 0.5127 for two of the tephra layers are interpreted as indicating that D'Entrecasteaux Islands volcanism younger than 2.9 Ma occasionally interacted with the Late Archean basement, possibly reflecting the mobilisation of the deep continental crust during active rift propagation.

Lithological and chemical composition, stages of sediment accumulation, and sedimentation rates in Core PSh24-2537, West Gotland Basin, Baltic Sea

We studied the grain-size, mineral and chemical compositions, physical properties, radiocarbon age, spore-pollen spectra, and diatom composition in sediments from Core PSh24-2537 sampled in the West Gotland Basin. Four lithological-stratigraphic units were distinguished: varved clays of the Baltic Ice Lake, black and black-gray (sulfide) clays of the Yoldian Sea, gray clays of Ancylus Lake, and greenish-gray sapropel-like littorine and post-littorine silts of the marine stage of Holocene. These units differ from each other both in their matter composition and in plant remains. In the littorine silts organic carbon concentra¬tion reached from 1.5 to 10.35%. Conditions of sediment accumulation and the stages of evolution of the West Gotland Basin over the post-glacial time are characterized.

A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

Non-equilibrium induction of tin in germanium: towards direct bandgap Ge1-xSnx nanowires

The development of non-equilibrium group IV nanoscale alloys is critical to achieving new functionalities, such as the formation of a direct bandgap in a conventional indirect bandgap elemental semiconductor. Here, we describe the fabrication of uniform diameter, direct bandgap Ge1-xSnx alloy nanowires, with a Sn incorporation up to 9.2[thinsp]at.%, far in excess of the equilibrium solubility of Sn in bulk Ge, through a conventional catalytic bottom-up growth paradigm using noble metal and metal alloy catalysts. Metal alloy catalysts permitted a greater inclusion of Sn in Ge nanowires compared with conventional Au catalysts, when used during vapour-liquid-solid growth. The addition of an annealing step close to the Ge-Sn eutectic temperature (230[thinsp][deg]C) during cool-down, further facilitated the excessive dissolution of Sn in the nanowires. Sn was distributed throughout the Ge nanowire lattice with no metallic Sn segregation or precipitation at the surface or within the bulk of the nanowires. The non-equilibrium incorporation of Sn into the Ge nanowires can be understood in terms of a kinetic trapping model for impurity incorporation at the triple-phase boundary during growth.

Chemical composition of tephra from the Greenland-Iceland-Norwegian-Sea

Explosive ocean island volcanism in the Greenland-Iceland-Norwegian Sea (GIN Sea) is indicated by marine tephra layers at 10-300 ka. Peaks of explosive volcanism occurred in oxygen isotope stages 8, 7, 5 and 1. The depositional age of the tephra was estimated using the oxygen isotope stratigraphy and dating of marine records. Geochemical analyses of the tephra layers show that all originate from Iceland. Here we report the characteristics of tephra from these major Icelandic events in 30 deep-sea cores from the GIN Sea. Our findings provide constraints on the distribution of tephra from the eruption source. For the Vedde Ash (oxygen isotope stage 1) we estimate a minimum fallout area of 2*10**5 km**2, stretching from central Greenland in the west and southern Sweden in the east, to 71°N in the GIN Sea. The magnitude of the eruption and the regional wind conditions controlled the extent and concentrations of these ash fallout events. Oceanic circulation and differential settling may have affected the distribution and final deposition of ash particles such as bubble wall shards.