Application of gel-casting to the fabrication of 1-3 piezoelectric ceramic-polymer composites for high-frequency ultrasound devices

A modified gel-casting technique was used to fabricate a 1-3 piezoelectric ceramic/polymer composite substrate formed by irregular-shaped pillar arrays of small dimensions and kerfs. This technique involves the polymerization of aqueous piezoelectric (PZT) suspensions with added water-soluble epoxy resin and polyamine-based hardener that lead to high strength, high density and resilient ceramic bodies. Soft micromoulding was used to shape the ceramic segments, and micropillars with lateral features down to 4 m and height-to-width aspect ratios of ∼10 were achieved. The composite exhibited a clear thickness resonance mode at approximately 70 MHz and a k eff ∼ 0.51, demonstrating that the ceramic micropillars possess good electrical properties. Furthermore, gel-casting allows the fabrication of ceramic structures with non-conventional shapes; hence, device design is not limited by the standard fabrication methods. This is of particular benefit for high-frequency transducers where the critical design dimensions are reduced. © 2012 IOP Publishing Ltd.

Polymer gate dielectrics with self-assembled monolayers for high-mobility organic thin-film transistors based on copper phthalocyanine

Organic thin-film transistors based on polycrystalline copper phthalocyanine (CuPc) were fabricated by using poly(vinyl alcohol) as gate dielectric. After treatment of the gate dielectric using an octadecyltrichlorosilane self-assembled monolayer, a mobility of up to 0.11 cm2/V∈s was achieved, which is comparable to that of single-crystal CuPc devices (0.1-1 cm2/V∈s). The surface morphology was analyzed and the possible reasons for the enhanced mobility are discussed. © 2009 Springer-Verlag.

Fabrication of high-aspect-ratio polymer microstructures and hierarchical textures using carbon nanotube composite master molds

Scalable and cost effective patterning of polymer structures and their surface textures is essential to engineer material properties such as liquid wetting and dry adhesion, and to design artificial biological interfaces. Further, fabrication of high-aspect-ratio microstructures often requires controlled deep-etching methods or high-intensity exposure. We demonstrate that carbon nanotube (CNT) composites can be used as master molds for fabrication of high-aspect-ratio polymer microstructures having anisotropic nanoscale textures. The master molds are made by growth of vertically aligned CNT patterns, capillary densification of the CNTs using organic solvents, and capillary-driven infiltration of the CNT structures with SU-8. The composite master structures are then replicated in SU-8 using standard PDMS transfer molding methods. By this process, we fabricated a library of replicas including vertical micro-pillars, honeycomb lattices with sub-micron wall thickness and aspect ratios exceeding 50:1, and microwells with sloped sidewalls. This process enables batch manufacturing of polymer features that capture complex nanoscale shapes and textures, while requiring only optical lithography and conventional thermal processing. © 2011 The Royal Society of Chemistry.

Fibers with integrated mechanochemical switches: minimalistic design principles derived from fibronectin.

Inspired by molecular mechanisms that cells exploit to sense mechanical forces and convert them into biochemical signals, chemists dream of designing mechanochemical switches integrated into materials. Using the adhesion protein fibronectin, whose multiple repeats essentially display distinct molecular recognition motifs, we derived a computational model to explain how minimalistic designs of repeats translate into the mechanical characteristics of their fibrillar assemblies. The hierarchy of repeat-unfolding within fibrils is controlled not only by their relative mechanical stabilities, as found for single molecules, but also by the strength of cryptic interactions between adjacent molecules that become activated by stretching. The force-induced exposure of cryptic sites furthermore regulates the nonlinearity of stress-strain curves, the strain at which such fibers break, and the refolding kinetics and fraction of misfolded repeats. Gaining such computational insights at the mesoscale is important because translating protein-based concepts into novel polymer designs has proven difficult.

Using mesoscopic models to design strong and tough biomimetic polymer networks

Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N in and N out, the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N out, with the higher value of N out providing a stronger material. We also find that, if N in is smaller than N out, the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials. © 2011 American Chemical Society.

A printable optical time-temperature integrator based on shape memory in a chiral nematic polymer network

An optical and irreversible temperature sensor (e.g., a time-temperature integrator) is reported based on a mechanically embossed chiral-nematic polymer network. The polymer consists of a chemical and a physical (hydrogen-bonded) network and has a reflection band in the visible wavelength range. The sensors are produced by mechanical embossing at elevated temperatures. A relative large compressive deformation (up to 10%) is obtained inducing a shift to shorter wavelength of the reflection band (>30 nm). After embossing, a temperature sensor is obtained that exhibits an irreversible optical response. A permanent color shift to longer wavelengths (red) is observed upon heating of the polymer material to temperatures above the glass transition temperature. It is illustrated that the observed permanent color shift is related to shape memory in the polymer material. The films can be printed on a foil, thus showing that these sensors are potentially interesting as time-temperature integrators for applications in food and pharmaceutical products. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strong carrier lifetime enhancement in GaAs nanowires coated with semiconducting polymer.

The ultrafast charge carrier dynamics in GaAs/conjugated polymer type II heterojunctions are investigated using time-resolved photoluminescence spectroscopy at 10 K. By probing the photoluminescence at the band edge of GaAs, we observe strong carrier lifetime enhancement for nanowires blended with semiconducting polymers. The enhancement is found to depend crucially on the ionization potential of the polymers with respect to the Fermi energy level at the surface of the GaAs nanowires. We attribute these effects to electron doping by the polymer which reduces the unsaturated surface-state density in GaAs. We find that when the surface of nanowires is terminated by native oxide, the electron injection across the interface is greatly reduced and such surface doping is absent. Our results suggest that surface engineering via π-conjugated polymers can substantially improve the carrier lifetime in nanowire hybrid heterojunctions with applications in photovoltaics and nanoscale photodetectors.