Large-scale parallel arrays of silicon nanowires via block copolymer directed self-assembly

Extending the resolution and spatial proximity of lithographic patterning below critical dimensions of 20 nm remains a key challenge with very-large-scale integration, especially if the persistent scaling of silicon electronic devices is sustained. One approach, which relies upon the directed self-assembly of block copolymers by chemical-epitaxy, is capable of achieving high density 1?:?1 patterning with critical dimensions approaching 5 nm. Herein, we outline an integration-favourable strategy for fabricating high areal density arrays of aligned silicon nanowires by directed self-assembly of a PS-b-PMMA block copolymer nanopatterns with a L(0) (pitch) of 42 nm, on chemically pre-patterned surfaces. Parallel arrays (5 × 10(6) wires per cm) of uni-directional and isolated silicon nanowires on insulator substrates with critical dimension ranging from 15 to 19 nm were fabricated by using precision plasma etch processes; with each stage monitored by electron microscopy. This step-by-step approach provides detailed information on interfacial oxide formation at the device silicon layer, the polystyrene profile during plasma etching, final critical dimension uniformity and line edge roughness variation nanowire during processing. The resulting silicon-nanowire array devices exhibit Schottky-type behaviour and a clear field-effect. The measured values for resistivity and specific contact resistance were ((2.6 ± 1.2) × 10(5)Ωcm) and ((240 ± 80) Ωcm(2)) respectively. These values are typical for intrinsic (un-doped) silicon when contacted by high work function metal albeit counterintuitive as the resistivity of the starting wafer (～10 Ωcm) is 4 orders of magnitude lower. In essence, the nanowires are so small and consist of so few atoms, that statistically, at the original doping level each nanowire contains less than a single dopant atom and consequently exhibits the electrical behaviour of the un-doped host material. Moreover this indicates that the processing successfully avoided unintentional doping. Therefore our approach permits tuning of the device steps to contact the nanowires functionality through careful selection of the initial bulk starting material and/or by means of post processing steps e.g. thermal annealing of metal contacts to produce high performance devices. We envision that such a controllable process, combined with the precision patterning of the aligned block copolymer nanopatterns, could prolong the scaling of nanoelectronics and potentially enable the fabrication of dense, parallel arrays of multi-gate field effect transistors.     

Surface chemistry of phosphorus-containing carbons of lignocellulosic origin

Activated carbon adsorbents were prepared by phosphoric acid activation of fruit stones in an argon atmosphere at various temperatures in the 400-1000 °C range and at different acid/precursor impregnation ratios (0.63-1.02). The surface chemistry of the carbons was investigated by elemental analysis, cation exchange capacity (CEC, measured by neutralization of NaOH with acidic surface groups), infrared spectroscopy and potentiometric titration. Porous structure was derived from adsorption isotherms (N₂ at −196 °C and CO₂ at 0 °C). It was demonstrated that all carbons show considerable cation exchange capacity, the maximum (CEC = 2.2 mmol g⁻¹) being attained at 800 °C, which coincides with the maximum contents of phosphorus and oxygen. The cation exchange properties of phosphoric acid activated carbons from fruit stones are chemically stable in very acidic and basic solutions. Proton affinity distributions of all carbons show the presence of three types of surface groups with pK at 2.0-3.3, 4.6-5.9 and 7.6-9.1. These pK ranges were ascribed primarily to: (a) phosphorus-containing and carboxylic groups; (b) lactonic groups, and (c) phenolic groups, respectively. Phosphoric acid activated carbons are microporous with a relatively small contribution of mesopores. A maximum BET surface area of 1740 m² g⁻¹ was attained at 400 °C.     

Thermal patterns in simple models of cylindrical reactors

The propagation of fronts and the emergence of spatiotemporal patterns on a cylindrically shaped thin catalytic reactor is simulated with a homogeneous model of a fixed catalytic bed, with characteristically large Lewis and Peclet numbers, and a first-order Arrhenius kinetics (i.e., thermokinetic model) which may be coupled with slow changes of catalytic activity (i.e., oscillatory kinetics). Planar fronts of the thermokinetic model may undergo symmetry breaking in the transversal direction only at relatively low Lewis number, but for high Le the front remains flat. Patterns due to oscillatory kinetics in reactors of high Le are shown, for the first time, to undergo symmetry breaking in the azimuthal direction when the perimeter is sufficiently large. The generic regular patterns simulated then are rotating multi-wave patterns of constant rotation-speed and oscillatory-‘firing’ ones, and theirs selection is highly sensitive to governing parameters and initial conditions. The results are organized in bifurcation diagrams showing the coexisting two-dimensional solutions with varying perimeter. Increasing convective velocity or reactor radius leads to symmetry breaking of regular patterns and the system may switch to chaos.     

Local and high-strength joining of transparent glass and glass-ceramics by femtosecond Bessel beam

The creation of robust joint among different materials with notably different coefficients of thermal expansion (CTE) is an urgent task for the development of the engineering, laser technology, and aerospace industry. In this regard, femtosecond laser welding is a promising technique for efficient adhesion-free bonding of transparent materials. This paper reports on the laser welding of laser phosphate glass (CTE = 110 × 10⁻⁷ K⁻¹) and spinel-based glass–ceramic (CTE = 50 × 10⁻⁷ K⁻¹) by the Bessel beam. Dependencies of weld geometric parameters on the pulse energy and scanning speed were investigated, and the laser exposure conditions were optimized for durable welding. The weld joints were tested on shear strength, which was shown to be as record high as up to 147 MPa. Atomic force microscopy, Raman spectroscopy, and elemental analysis were used to investigate the structure and morphology of the weld after its fracture, which revealed the laser-induced amorphization of glass–ceramics and the formation of strong interconnection by laser-driven mutual diffusion of two glassy phases. The results demonstrate the prospects for using femtosecond lasers for efficient industrial welding of a wide range of materials.     

Mass transfer around prolate spheroidal drops in an extensional flow

Mass transfer in the continuous phase around a small eccentricity prolate spheroidal drop in an axisymmetric extensional creeping flow and at large Peclet numbers was investigated theoretically. The results show that, at very short times, the total quantity of solute transferred to or from the drop represents, at O(Ca¹), mass transfer by diffusion only around a sphere. For long times, or at steady‐state, the total quantity of solute transferred is, at O(Ca¹), slightly smaller than that of a spherical drop, and it decreases with an increase of the capillary number or the viscosity ratio. © 2012 Canadian Society for Chemical Engineering     

Oxidative Folding of Peptides with Cystine‐Knot Architectures: Kinetic Studies and Optimization of Folding Conditions

Bioactive peptides often contain several disulfide bonds that provide the main contribution to conformational rigidity and structural, thermal, or biological stability. Among them, cystine‐knot peptides—commonly named “knottins”—make up a subclass with several thousand natural members. Hence, they are considered promising frameworks for peptide‐based pharmaceuticals. Although cystine‐knot peptides are available through chemical and recombinant synthetic routes, oxidative folding to afford the bioactive isomers still remains a crucial step. We therefore investigated the oxidative folding of ten protease‐inhibiting peptides from two knottin families, as well as that of an HIV entry inhibitor and of aprotinin, under two conventional sets of folding conditions and by a newly developed procedure. Kinetic studies identified folding conditions that resulted in correctly folded miniproteins with high rates of conversion even for highly hydrophobic and aggregation‐prone peptides in concentrated solutions.     

Structural Study of the Partially Disordered Full‐Length δ Subunit of RNA Polymerase from Bacillus subtilis

The partially disordered δ subunit of RNA polymerase was studied by various NMR techniques. The structure of the well‐folded N‐terminal domain was determined based on inter‐proton distances in NOESY spectra. The obtained structural model was compared to the previously determined structure of a truncated construct (lacking the C‐terminal domain). Only marginal differences were identified, thus indicating that the first structural model was not significantly compromised by the absence of the C‐terminal domain. Various ¹⁵N relaxation experiments were employed to describe the flexibility of both domains. The relaxation data revealed that the C‐terminal domain is more flexible, but its flexibility is not uniform. By using paramagnetic labels, transient contacts of the C‐terminal tail with the N‐terminal domain and with itself were identified. A propensity of the C‐terminal domain to form β‐type structures was obtained by chemical shift analysis. Comparison with the paramagnetic relaxation enhancement indicated a well‐balanced interplay of repulsive and attractive electrostatic interactions governing the conformational behavior of the C‐terminal domain. The results showed that the δ subunit consists of a well‐ordered N‐terminal domain and a flexible C‐terminal domain that exhibits a complex hierarchy of partial ordering.     

A Water Cyclone to Preserve Insoluble Aerosols in Liquid Flow—An Interface to Flow Cytometry to Detect Airborne Nucleic Acid

A miniature cyclone was designed to gently capture fine aerosols into a continuous liquid flow. The geometry of the cyclone was designed so that the friction of the turning air swirls a 100 μl volume of water at the base of the cone, creating a standing liquid vortex which coats the inside deposition surface. The collection efficiency of the cyclone was characterized as a function of insoluble particle size, both in stand-alone operation and preceded by aerosol growth by water vapor condensation. The aerosol growth lowered the smallest collected particle size and created synonymous sample-into-substrate material conditions at the point of impact. The cyclone collection efficiencies were higher than 88% for the fluorescent polystyrene latex bead diameter sizes 50–3000 nm. The cyclone was further interfaced to a flow cytometer to detect airborne nucleic acid (as a virus test aerosol) in the cyclone sample flow. The flow cytometer, which is commonly used for single cell identification via fluorescence, was modified to accept a continuous sample flow (nominal 60 μl min^?1) from the cyclone for real-time detection. A rod-shaped plant virus (Tobamovirus) and a protein-enveloped insect virus (Baculovirus) were aerosolized, collected by the cyclone, and stained inline using the nucleic acid dyes SYBR Green I, SYTO-9, and SYTO-24 (Molecular Probes, Inc.). In addition, an Environmental Scanning Electron Microscope (ESEM) was used to confirm the collection of single virus particles and qualitatively evaluate the degree to which the aerosolization and collection process affected the integrity of the virus.     

Influence of residual solvent on physical and chemical properties of amorphous glassy polymer films

One of the most important areas of current research is the study of the influence of the prehistory of samples of amorphous glassy polymers on their physical and chemical properties. The study of structural changes by high temperature IR spectroscopy compared with of quantum chemical calculations allows for an understanding of the mechanism and nature of such processes. The changes in the structure of the polymer chain depending on the type of solvent used in the formation of the films are demonstrated using the examples of several different classes of polymers. In turn, the impact of such changes in the structure on the physical and chemical properties of the polymer films is demonstrated. © 2013 Society of Chemical Industry