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.

Sorting nanoparticles by centrifugal fields in clean media

The on-demand availability of nanomaterials with selected size and well-defined chemical/physical properties is of fundamental importance for their widespread application. We report two clean, rapid, and non-destructive approaches for nanoparticle (NP) size selection in centrifugal fields. The first exploits rate zonal separation in a high viscosity gradient. The second exploits selective sedimentation of NPs with different sizes. These methods are here applied to metallic nanoparticles (MNPs) with different compositions and surface chemistry, dispersed either in water or organic solvents. The approach is general and can also be exploited for the separation of NPs of any material. We selectively sort both Au and AgNPs with sizes in the 10-30 nm range, achieving chemical-free MNPs with low polydispersivity. We do not use solutes, thus avoiding contamination, and only require low centrifugal fields, easily achievable in benchtop systems. © 2013 American Chemical Society.

Centrifuge coating for low-waste solution processing of transparent nanostructured electrodes

Centrifuge coating was implemented to fabricate nanostructured conductive layers through solution processing at room temperature. This coating procedure allows fast evaporation, thereby fixing the nanomaterials in their dispersed state onto a substrate by the centrifuge action. Material wastes were minimized by mitigating the effects of particle reaggregation. Using this method, we fabricate single-wall nanotube coatings on different substrates such as polyethylene terephthalate, polydimethylsiloxane, and an acrylic elastomer with no prior surface modification of the substrate. The effects of the choice of solvents on the morphology and subsequent performance of the coating network are studied. © 2002-2012 IEEE.

Optical investigations of the effect of solvent and thermal annealing on the optoelectronic properties of Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) films

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most promising conducting polymers that can be used as transparent electrode or as buffer layer for organic electronic devices. However, when used as an electrode, its conductivity has to be optimized either by the addition of solvents or by post-deposition processing. In this work, we investigate the effect of the addition of the polar solvent dimethylsulfoxide (DMSO) to an aqueous PEDOT:PSS solution on its optical and electrical properties by the implementation of the Drude model for the analysis of the measured pseudo-dielectric function by Spectroscopic Ellipsometry from the near infrared to the visible-far ultraviolet spectral range. The results show that the addition of DMSO increases significantly the film conductivity, which reaches a maximum value at an optimum DMSO concentration as it has confirmed by experimentally measured conductivity values. The post-deposition thermal annealing has been found to have a smaller effect on the film conductivity. © 2013 Elsevier B.V.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Pulsed laser writing of holographic nanosensors

Tuneable optical sensors have been developed to sense chemical stimuli for a range of applications from bioprocess and environmental monitoring to medical diagnostics. Here, we present a porphyrin-functionalised optical sensor based on a holographic grating. The holographic sensor fulfils two key sensing functions simultaneously: it responds to external stimuli and serves as an optical transducer in the visible region of the spectrum. The sensor was fabricated via a 6 nanosecond-pulsed laser (350 mJ, λ = 532 nm) photochemical patterning process that enabled a facile fabrication. A novel porphyrin derivative was synthesised to function as the crosslinker of a polymer matrix, the light-absorbing material, the component of a diffraction grating, as well as the cation chelating agent in the sensor. The use of this multifunctional porphyrin permitted two-step fabrication of a narrow-band light diffracting photonic sensing structure. The resulting structure can be tuned finely to diffract narrow-band light based on the changes in the fringe spacing within the polymer and the system's overall index of refraction. We show the utility of the sensor by demonstrating its reversible colorimetric tuneability in response to variation in concentrations of organic solvents and metal cations (Cu 2+ and Fe2+) in the visible region of the spectrum (λmax ≈ 520-680 nm) with a response time within 50 s. Porphyrin-functionalised optical sensors offer great promise in fields varying from environmental monitoring to biochemical sensing to printable optical devices. This journal is © the Partner Organisations 2014.