Orientation Control of Block Copolymers Using Surface Active, Phase-Preferential Additives.

Orientation control of thin film nanostructures derived from block copolymers (BCPs) are of great interest for various emerging technologies like separation membranes, nanopatterning, and energy storage. While many BCP compositions have been developed for these applications, perpendicular orientation of these BCP domains is still very challenging to achieve. Herein we report on a new, integration-friendly approach in which small amounts of a phase-preferential, surface active polymer (SAP) was used as an additive to a polycarbonate-containing BCP formulation to obtain perpendicularly oriented domains with 19 nm natural periodicity upon thermal annealing. In this work, the vertically oriented BCP domains were used to demonstrate next generation patterning applications for advanced semiconductor nodes. Furthermore, these domains were used to demonstrate pattern transfer into a hardmask layer via commonly used etch techniques and graphoepitaxy-based directed self-assembly using existing lithographic integration schemes. We believe that this novel formulation-based approach can easily be extended to other applications beyond nanopatterning.

Wettability control and flow regulation using a nanostructure-embedded surface.

This work addresses the synthesis, integration and characterization of a nanostructure-embedded thermoresponsive surface for flow regulation. In order to create a hierarchic structure which consists of microscale texture and nanoscale sub-texture, hybrid multilayers consisting of poly(allylamine hydrochloride) (PAH), poly(acrylic acid) (PAA) and colloidal silica nanoparticles (average diameter = 22 nm and 7 nm) were used. Based on the electrostatic interactions between the polyelectrolytes and nanoparticles, a layer-by-layer deposition technique in combination with photolithography was employed to obtain a localized, conformally-coated patch in a microchannel. Grafted with the thermoresponsive polymer, poly(N-isopropylacrylamide) (PNIPAAm), wettability of the surface could be tuned upon heating or cooling. The measurement of differential pressure at various stages of device verified the working conditions of the nanostructure-embedded surface for regulating a capillary flow in the microchannel.

Reduced Graphene Oxide/Poly(3-hexylthiophene) Supramolecular Composites.

Poly(3-hexylthiophene) (P3HT) supramolecular structures are fabricated on P3HT-dispersed reduced graphene oxide (RGO) monolayers and surfactant-free RGO monolayers. P3HT is able to disperse RGO in hot anisole/N,N-dimethylformamide solvents, and forms nanowires on RGO surfaces through a RGO induced crystallization process. The TEM and AFM investigation of the resultant P3HT/RGO composites shows that P3HT nanowires grow from RGO, and connect individual RGO monolayers. Raman spectroscopy confirms the interaction between P3HT and RGO, which allows the manipulation of the RGO electrical properties. Such a bottom-up approach provides interesting graphene-based composites for nanometer-scale electronics.

Patterning of diverse mammalian cell types in serum free medium with photoablation.

Integration of living cells with novel microdevices requires the development of innovative technologies for manipulating cells. Chemical surface patterning has been proven as an effective method to control the attachment and growth of diverse cell populations. Patterning polyelectrolyte multilayers through the combination of layer-by-layer self-assembly technique and photolithography offer a simple, versatile, and silicon compatible approach that overcomes chemical surface patterning limitations, such as short-term stability and low-protein adsorption resistance. In this study, direct photolithographic patterning of two types of multilayers, PAA (poly acrylic acid)/PAAm (poly acryl amide) and PAA/PAH (poly allyl amine hydrochloride), were developed to pattern mammalian neuronal, skeletal, and cardiac muscle cells. For all studied cell types, PAA/PAAm multilayers behaved as a cytophobic surface, completely preventing cell attachment. In contrast, PAA/PAH multilayers have shown a cell-selective behavior, promoting the attachment and growth of neuronal cells (embryonic rat hippocampal and NG108-15 cells) to a greater extent, while providing little attachment for neonatal rat cardiac and skeletal muscle cells (C2C12 cell line). PAA/PAAm multilayer cellular patterns have also shown a remarkable protein adsorption resistance. Protein adsorption protocols commonly used for surface treatment in cell culture did not compromise the cell attachment inhibiting feature of the PAA/PAAm multilayer patterns. The combination of polyelectrolyte multilayer patterns with different adsorbed proteins could expand the applicability of this technology to cell types that require specific proteins either on the surface or in the medium for attachment or differentiation, and could not be patterned using the traditional methods.

Fabrication of ultrathin polyelectrolyte fibers and their controlled release properties.

Ultrathin fibers comprising 2-weak polyelectrolytes, poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) were fabricated using the electrospinning technique. Methylene blue (MB) was used as a model drug to evaluate the potential application of the fibers for drug delivery. The release of MB was controlled in a nonbuffered medium by changing the pH of the solution. The sustained release of MB in a phosphate buffered saline (PBS) solution was achieved by constructing perfluorosilane networks on the fiber surfaces as capping layers. Temperature controlled release of MB was obtained by depositing temperature sensitive PAA/poly(N-isopropylacrylamide) (PNIPAAM) multilayers onto the fiber surfaces. The controlled release of drugs from electrospun fibers have potential applications as drug carriers in biomedical science.