A vertical lamellae arrangement of sub-16 nm pitch (domain spacing) in a microphase separated PS-b-PEO thin film by salt addition

Ultra-small feature size (∼8 nm domain width) nanopatterns have been achieved using a symmetric polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer (BCP) of low molecular weight (PS and PEO blocks of 5.5 and 5.3 kg mol−1 respectively). The work represents the smallest feature size attained and the first observation of a well-controlled film of a perpendicularly oriented lamellar pattern in thin film form for this system. The polymer synthesized and described herein has a value χN (=7.7), below the expected BCP phase segregation limit of 10.5. These patterns were achieved by amplification of the effective interaction parameter (χeff) of the BCP system by the addition of lithium chloride (LiCl) salt. A model where the Li+ ions strongly coordinate with the PEO block without affecting the PS chain is proposed to explain the ordered self-assembly. The morphological and structural evolution for these PS-b-PEO/LiCl thin films was investigated by variation of the experimental parameters such as temperature, annealing time, salt concentrations, solution aging time, annealing solvent etc. All the experimental parameters have significant effects on the morphology, domain spacing, defectivity or surface roughness of these symmetric BCP thin films as evident from different microscopic and spectroscopic techniques. Possible hard mask applications in the area of lithography are demonstrated

Fabrication of ultra-dense sub-10 nm in-plane Si nanowire arrays by using a novel block copolymer method: optical properties

The use of a low-χ, symmetric block copolymer as an alternative to the high-χ systems currently being translated towards industrial silicon chip manufacture has been demonstrated. Here, the methodology for generating on-chip, etch resistant masks and subsequent pattern transfer to the substrate using ultra-small dimension, lamellar, microphase separated polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) is described. Well-controlled films of a perpendicularly oriented lamellar pattern with a domain size of ∼8 nm were achieved through amplification of an effective interaction parameter (χeff) of the BCP system. The self-assembled films were used as ‘templates’ for the generation of inorganic oxides nanowire arrays through selective metal ion inclusion and subsequent processing. Inclusion is a significant challenge because the lamellar systems have less chemical and mechanical robustness than the cylinder forming materials. The oxide nanowires of uniform diameter (∼8 nm) were isolated and their structure mimics the original BCP nanopatterns. We demonstrate that these lamellar phase iron oxide nanowire arrays could be used as a resist mask to fabricate densely packed, identical ordered, good fidelity silicon nanowire arrays on the substrate. Possible applications of the materials prepared are discussed, in particular, in the area of photonics and photoluminescence where the properties are found to be similar to those of surface-oxidized silicon nanocrystals and porous silicon

Carbon nanostructures derived through hypergolic reaction of conductive polymers with fuming nitric acid at ambient conditions

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.Web of Science266art. no. 159

Microwave synthesis, characterization and perspectives of wood pencil-derived carbon

More than 14 billion pencils are manufactured and used globally every year. On average, a pencil is discarded after 60% of its original length has been depleted. In the present work we propose a simple and affordable way of converting this non-neglectable amount of waste into added value carbon product. In particular, we demonstrate the microwave synthesis of carbon from the wood pencil with and without chemical activation. This could be a process stage before the final recycling of the expensive graphite core. In the latter case, irradiation of the wood pencil in a domestic microwave oven heats up the pencil's graphite core, thus inducing carbonization of its wood casing. The carbonized product consists of amorphous carbon nanosheets having relatively low surface area. However, if the wood pencil is soaked in 50% KOH aqueous solution prior to microwave irradiation, a significantly higher surface area of carbon is obtained, consisting of irregular-shaped porous particles. Consequently, the obtained carbon can easily decolorize a methylene blue aqueous solution, can be used to make pocket warmers or gunpowder, and lastly, serves as an excellent adsorbent towards Cr(VI) removal from water, showing a maximum adsorption capacity of 70-75 mg/g within 24 h at 23 degrees C, pH = 3.Web of Science121art. no. 41

Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes

The synthesis, molecular and morphological characterization of a 3-miktoarm star terpolymer of polystyrene (PS, M¯¯¯¯n = 61.0 kg/mol), polybutadiene (PB, M¯¯¯¯n = 38.2 kg/mol) and polyisoprene (PI, M¯¯¯¯n = 29.2 kg/mol), corresponding to volume fractions (φ) of 0.46, 0.31 and 0.23 respectively, was studied. The major difference of the present material from previous ABC miktoarm stars (which is a star architecture bearing three different segments, all connected to a single junction point) with the same block components is the high 3,4-microstructure (55%) of the PI chains. The interaction parameter and the degree of polymerization of the two polydienes is sufficiently positive to create a three-phase microdomain structure as evidenced by differential scanning calorimetry and transmission electron microscopy (TEM). These results in combination with small-angle X-ray scattering (SAXS) and birefringence experiments suggest a cubic tricontinuous network structure, based on the I4132 space group never reported previously for such an architecture

A vertical lamellae arrangement of sub-16 nm pitch (domain spacing) in a microphase separated PS-b-PEO thin film by salt addition

Ultra-small feature size (∼8 nm domain width) nanopatterns have been achieved using a symmetric polystyrene-b-polyethylene oxide (PS-b-PEO) block copolymer (BCP) of low molecular weight (PS and PEO blocks of 5.5 and 5.3 kg mol−1 respectively). The work represents the smallest feature size attained and the first observation of a well-controlled film of a perpendicularly oriented lamellar pattern in thin film form for this system. The polymer synthesized and described herein has a value χN (=7.7), below the expected BCP phase segregation limit of 10.5. These patterns were achieved by amplification of the effective interaction parameter (χeff) of the BCP system by the addition of lithium chloride (LiCl) salt. A model where the Li+ ions strongly coordinate with the PEO block without affecting the PS chain is proposed to explain the ordered self-assembly. The morphological and structural evolution for these PS-b-PEO/LiCl thin films was investigated by variation of the experimental parameters such as temperature, annealing time, salt concentrations, solution aging time, annealing solvent etc. All the experimental parameters have significant effects on the morphology, domain spacing, defectivity or surface roughness of these symmetric BCP thin films as evident from different microscopic and spectroscopic techniques. Possible hard mask applications in the area of lithography are demonstrated

Fabrication of ultra-dense sub-10 nm in-plane Si nanowire arrays by using a novel block copolymer method: optical properties

The use of a low-χ, symmetric block copolymer as an alternative to the high-χ systems currently being translated towards industrial silicon chip manufacture has been demonstrated. Here, the methodology for generating on-chip, etch resistant masks and subsequent pattern transfer to the substrate using ultra-small dimension, lamellar, microphase separated polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) is described. Well-controlled films of a perpendicularly oriented lamellar pattern with a domain size of ∼8 nm were achieved through amplification of an effective interaction parameter (χeff) of the BCP system. The self-assembled films were used as ‘templates’ for the generation of inorganic oxides nanowire arrays through selective metal ion inclusion and subsequent processing. Inclusion is a significant challenge because the lamellar systems have less chemical and mechanical robustness than the cylinder forming materials. The oxide nanowires of uniform diameter (∼8 nm) were isolated and their structure mimics the original BCP nanopatterns. We demonstrate that these lamellar phase iron oxide nanowire arrays could be used as a resist mask to fabricate densely packed, identical ordered, good fidelity silicon nanowire arrays on the substrate. Possible applications of the materials prepared are discussed, in particular, in the area of photonics and photoluminescence where the properties are found to be similar to those of surface-oxidized silicon nanocrystals and porous silicon

Functionally graded poly(dimethylsiloxane)/silver nanocomposites with tailored broadband optical absorption

© 2014 Elsevier B.V. All rights reserved. In this work, we produce functionally graded nanocomposites consisting of silver (Ag) plasmonic nanoparticles (PNPs) supported in a poly(dimethylsiloxane) (PDMS) matrix. PDMS was selected due to its high optical transparency, nontoxicity and ease of use. The Ag PNPs were formed by annealing sputtered Ag ultra-thin films and were subsequently capped by a spin-coated PDMS layer. We investigate the factors that affect their plasmonic behavior, such as the PNP size, the annealing conditions and the surrounding environment. In order to achieve broadband absorption, we developed PDMS/Ag(PNPs) multilayers with graded PNP size. Thus, we demonstrate the significance of the stacking sequence of various plasmonic layers sandwiched between PDMS layers and its potential for tailoring the plasmonic response of multilayer structure. As a demonstration of this approach, we deposited a specially designed multilayer structure, whose optical extinction resembles the solar emission spectrum

Toward Strong Thermoplastic Elastomers with Asymmetric Miktoarm Block Copolymer Architectures

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