Self-organization and dynamics of nanoparticles in chemically active plasmas for low-temperature deposition of silicon and carbon-based nanostructured films

Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C 2H2), and octafluorocyclobutane (c-C4F 8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.

Third harmonic generation of the surface wave in the semiconductor-metal slowing-down structure

A nonlinear process is considered of the surface wave third harmonics generation in a slowing-down semiconductor-metal structure. The process is conditioned by non-parabolicity of the charge carrier dispersion law. It is shown that in narrow-gap semiconducting materials it is necessary to account for the process together with the surface wave second harmonics generation conditioned by nonlinearity of quasi-hydrodynamics and the Maxwell equations. The conclusion is made that the third harmonies amplitude in narrow-gap semiconductors may exceed substantially the signal amplitude at the 3w frequency in a gas plasma and be of the same order with the surface waves second harmonies amplitude.

Parametric excitation of high-frequency surface waves in a plasma-metal waveguide structure

The problem concerning the excitation of high-frequency surface waves (SW) propagating across an external magnetic field at a plasma-metal interface is considered. A homogeneous electric pump field is applied in the direction transverse with respect to the plasma-metal interface. Two high-frequency SW from different frequency ranges of existence and propagating in different directions are shown to be excited in this pump field. The instability threshold pump-field values and increments are obtained for different parameters of the considered waveguide structure. The results associated with saturation of the nonlinear instability due to self-interaction effects of the excited SW are given as well. The results are appropriate for both gaseous and semiconductor plasmas.

Two-channel waveguide modulator based on surface wave propagating in a semiconductor-metal thin-film structure

The results of theoretical investigations of two-channel waveguide modulator based on Surface Wave (SW) propagation are presented. The structure studied consists of two n-type semiconductor waveguide channels separated from each other by a dielectric gap and coated by a metal. The SW propagates at the semiconductor-metal interface across an external magnetic field which is parallel to the interface. An external dc voltage is applied to the metal surface of one channel to provide a small phase shift between two propagating modes. In a coupled mode approximation, two possible regimes of operation of the structure, namely as a directional coupler and as an electro-optical modulator, are considered. Our results suggest new applications in millimeter and submillimeter wave solid-state electronics and integrated optics.

How should future building structure and emergency response cope with bushfire attack?

Bushfires are regular occurrences in the Australian landscape which can, under adverse weather conditions, give rise to losses of life, property, infrastructure, environmental and cultural values. Where property loss is involved, historical surveys of house losses have focussed on ember, radiant heat and flame contact as key bushfire attack mechanisms. Although often noted, little work has been done to quantify the impact of fire generated or fire enhanced wind and pyro-convective events on house loss and to improve construction practice within Australia. It is well known that strong winds are always associated with bushfire events. It is less well known, although increasingly shown through anecdotal evidence, that bushfires are not a passive companion of wind, but indeed they interact with winds and can together cause significant damages to exposed buildings and ecological structures. Previous studies have revealed the effects of wind, fire and structure interactions with the result of increased pressure coefficient distributions on the windward side of a building downstream of a fire front. This paper presents a further analysis of the result in relations to the relevant standards and fire weather conditions. A review of wind code and bushfire code was conducted. Based on the result of the current study, the authors believe it is necessary to consider wind as an attack mechanism in bushfire events. The results of the study will also have implications on bushfire emergency management, design of emergency shelters, perception of danger, emergency evacuation and on risk assessment.

Structure-mediated thermal transport of monolayer graphene allotropes nanoribbons

We report the study of the thermal transport management of monolayer graphene allotrope nanoribbons (size ∼20 × 4 nm2) by the modulation of their structures via molecular dynamics simulations. The thermal conductivity of graphyne (GY)-like geometries is observed to decrease monotonously with increasing number of acetylenic linkages between adjacent hexagons. Strikingly, by incorporating those GY or GY-like structures, the thermal performance of graphene can be effectively engineered. The resulting hetero-junctions possess a sharp local temperature jump at the interface, and show a much lower effective thermal conductivity due to the enhanced phonon–phonon scattering. More importantly, by controlling the percentage, type and distribution pattern of the GY or GY-like structures, the hetero-junctions are found to exhibit tunable thermal transport properties (including the effective thermal conductivity, interfacial thermal resistance and rectification). This study provides a heuristic guideline to manipulate the thermal properties of 2D carbon networks, ideal for application in thermoelectric devices with strongly suppressed thermal conductivity.

Assembly and self-organization of nanomaterials

The increasing interest in nanoscience and nanotechnology has prompted intense investigations into appropriate fabrication techniques. Self-organized, bottom-up growth of nanomaterials using plasma nanofabrication techniques1–10 has proven to be one of the most promising approaches for the construction of precisely tailored nanostructures (i.e., quantum dots,11–13 nanotubes,14–17 nanowires,18–20 etc.) arrays. Thus the primary aim of this chapter is to show how plasmas may be used to achieve a high level of control during the self-organized growth of a range of nanomaterials, from zero-dimensional quantum dots (Section 15.2) to one- and two-dimensional nanomaterials (Section 15.3) to nanostructured films (Section 15.4)...

Spectroscopic vibrations of austinite (CaZnAsO4⋅OH) and its mineral structure : Implications for identification of secondary arsenic-containing mineral

Austinite (CaZnAsO4⋅OH) is a unique secondary mineral in arsenic-contaminated mine wastes. The infrared and Raman spectroscopies were used to characterize the austenite vibrations. The IR bands at 369, 790 and 416 cm−1 are assigned to the ν2, ν3 and ν4 vibrations of AsO43− unit, respectively. The Raman bands at 814, 779 and 403 cm−1 correspond to the ν1, ν3 and ν4 vibrations of AsO43− unit respectively. The sharp bands at 3265 cm−1 for IR and 3270 cm−1 both reveals that the structural hydroxyl units exist in the austenite structure. The IR and Raman spectra both show that some SO4 units isomorphically replace AsO4 in austinite. X-ray single crystal diffraction provides the arrangement of each atom in the mineral structure, and also confirms that the conclusions made from the vibrational spectra. Micro-powder diffraction was used to confirm our mineral identification due to the small quantity of the austenite crystals.

Structure and assembly of immature HIV

The major structural components of HIV are synthesized as a 55-kDa polyprotein, Gag. Particle formation is driven by the self-assembly of Gag into a curved hexameric lattice, the structure of which is poorly understood. We used cryoelectron tomography and contrast-transfer-function corrected subtomogram averaging to study the structure of the assembled immature Gag lattice to approximate to 17-angstrom resolution. Gag is arranged in the immature virus as a single, continuous, but incomplete hexameric lattice whose curvature is mediated without a requirement for pentameric defects. The resolution of the structure allows positioning of individual protein domains. High-resolution crystal structures were fitted into the reconstruction to locate protein-protein interfaces involved in Gag assembly, and to identify the structural transformations associated with virus maturation. The results of this study suggest a concept for the formation of nonsymmetrical enveloped viruses of variable sizes.

High mobility diketopyrrolopyrrole (DPP)-based organic semiconductor materials for organic thin film transistors and photovoltaics

In recent years, the electron-accepting diketopyrrolopyrrole (DPP) moiety has been receiving considerable attention for constructing donor-acceptor (D-A) type organic semiconductors for a variety of applications, particularly for organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Through association of the DPP unit with appropriate electron donating building blocks, the resulting D-A molecules interact strongly in the solid state through intermolecular D-A and π-π interactions, leading to highly ordered structures at the molecular and microscopic levels. The closely packed molecules and crystalline domains are beneficial for intermolecular and interdomain (or intergranular) charge transport. Furthermore, the energy levels can be readily adjusted, affording p-type, n-type, or ambipolar organic semiconductors with highly efficient charge transport properties in OTFTs. In the past few years, a number of DPP-based small molecular and polymeric semiconductors have been reported to show mobility close to or greater than 1 cm2 V -1 s-1. DPP-based polymer semiconductors have achieved record high mobility values for p-type (hole mobility: 10.5 cm2 V-1 s-1), n-type (electron mobility: 3 cm2 V-1 s-1), and ambipolar (hole/electron mobilities: 1.18/1.86 cm2 V-1 s-1) OTFTs among the known polymer semiconductors. Many DPP-based organic semiconductors have favourable energy levels and band gaps along with high hole mobility, which enable them as promising donor materials for OPVs. Power conversion efficiencies (PCE) of up to 6.05% were achieved for OPVs using DPP-based polymers, demonstrating their potential usefulness for the organic solar cell technology. This article provides an overview of the recent exciting progress made in DPP-containing polymers and small molecules that have shown high charge carrier mobility, around 0.1 cm2 V-1 s-1 or greater. It focuses on the structural design, optoelectronic properties, molecular organization, morphology, as well as performances in OTFTs and OPVs of these high mobility DPP-based materials.

Supramolecular organization in fluorene/indenofluorene-oligothiophene alternating conjugated copolymers

A series of conjugated copolymers containing fluorene or indenofluorene units alternating with oligothiophene segments, with potential interest for use as the active layer in field-effect transistors, is investigated. Atomic force microscopy analysis of the morphology of thin deposits shows either the formation of fibrillar structures, which are the signature of long-range π stacking, or the presence of untextured aggregates, resulting from disordered assembly. These morphologies are interpreted in terms of the supramolecular organization of the conjugated chains. Molecular modeling simulations indicate that the commensurability between the lengths of the monomer units and the presence of alkyl side groups are the two key structural factors governing the chain organization into highly ordered assemblies. The most favorable structures are those combining fluorene (indenofluorene) units with unsubstituted bithiophene (terthiophene) segments.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.

The SOLO Taxonomy as a means of shaping and assessing learning in higher education

This paper is a discussion of the use of the SOLO (Structure of Observed Learning Outcomes) Taxonomy (Biggs & Collis, 1982, 1989; Biggs, 1991, 1992a, 1992b; Boulton‐Lewis, 1992, 1994) as a means of developing and assessing higher order thinking in Higher Education. It includes a summary of the research into its use to date as an instrument to find out what students know and believe about their own learning, to assess entering knowledge in a discipline, to present examples of structural organization of knowledge in a discipline, to provide models of levels of desired learning outcomes, and in particular to assess learning outcomes. A proposal is made for further research.

Isolation, structure determination and cytotoxicity studies of tryptophan alkaloids from an Australian marine sponge Hyrtios sp

Mass-guided fractionation of the MeOH extract from a specimen of the Australian marine sponge Hyrtios sp. resulted in the isolation of two new tryptophan alkaloids, 6-oxofascaplysin (2), and secofascaplysic acid (3), in addition to the known metabolites fascaplysin (1) and reticulatate (4). The structures of all molecules were determined following NMR and MS data analysis. Structural ambiguities in 2 were addressed through comparison of experimental and DFT-generated theoretical NMR spectral values. Compounds 1–4 were evaluated for their cytotoxicity against a prostate cancer cell line (LNCaP) and were shown to display IC50 values ranging from 0.54 to 44.9 μM.