Blending Linear and Cyclic Block Copolymers to Manipulate Nanolithographic Feature Dimensions.

Block copolymers (BCPs) consist of two or more covalently bound chemically distinct homopolymer blocks. These macromolecules have emerging applications in photonics, membrane separations, and nanolithography stemming from their self-assembly into regular nanoscale structures. Theory suggests that cyclic BCPs should form features up to 40% smaller than their linear analogs while also exhibiting superior thin-film stability and assembly dynamics.

Aerosol Acidity Sensing via Polymer Degradation.

The acidity of atmospheric aerosols is a critical property that affects the chemistry and composition of the atmosphere. Many key multiphase chemical reactions are pH-dependent, impacting processes like secondary organic aerosol formation, and need to be understood at a single particle level due to differences in particle-to-particle composition that impact both climate and health. However, the analytical challenge of measuring aerosol acidity in individual particles has limited pH measurements for fine (<2.

Anomalous Potential-Dependent Friction on Au(111) Measured by AFM.

We present an exploratory study of the tribological properties between an AFM probe and a Au(111) surface in an aqueous environment while subjected to applied surface potentials. Using a three-electrode setup, the electrical potential and interfacial electric field on a Au(111) working electrode are controlled. Lateral force microscopy is used to measure the friction forces between the AFM probe and the Au surface.

Enhanced Adhesion of Mosquitoes to Rough Surfaces.

Insects and small animals capable of adhering reversibly to a variety of surfaces employ the unique design of the distal part of their legs. In the case of mosquitoes, their feet are composed of thousands of micro- and nanoscale protruding structures, which impart superhydrophobic properties. Previous research has shown that the superhydrophobic nature of the feet allows mosquitoes to land on water, which is necessary for their reproduction cycle.

Stimuli-responsive copolymer solution and surface assemblies for biomedical applications.

Stimuli-responsive polymeric materials is one of the fastest growing fields of the 21st century, with the annual number of papers published more than quadrupling in the last ten years. The responsiveness of polymer solution assemblies and surfaces to biological stimuli (e.g.

Systematic study on the effect of solvent removal rate on the morphology of solvent vapor annealed ABA triblock copolymer thin films.

Nanoscale self-assembly of block copolymer thin films has garnered significant research interest for nanotemplate design and membrane applications. To fulfill these roles, control of thin film morphology and orientation is critical. Solvent vapor annealing (SVA) treatments can be used to kinetically trap morphologies in thin films not achievable by traditional thermal treatments, but many variables affect the outcome of SVA, including solvent choice, total solvent concentration/swollen film thickness, and solvent removal rate.

Controlled vapor deposition approach to generating substrate surface energy/chemistry gradients.

Substrate surface energy/chemistry gradients provide a means for high-throughput exploration of the surface interactions that are important in many chemical and biological processes. We describe the implementation of a controlled vapor deposition approach to surface modification that enables the facile production of substrate surface energy/chemistry gradients while maintaining versatility in both the gradient profile and the surface chemistry. In our system, gradient formation relies on the cross-deposition of functionalized chlorosilanes onto the substrate surface via vaporization of the deposition materials from liquid reservoirs under dynamic vacuum.

Gradient solvent vapor annealing of block copolymer thin films using a microfluidic mixing device.

Solvent vapor annealing (SVA) with solvent mixtures is a promising approach for controlling block copolymer thin film self-assembly. In this work, we present the design and fabrication of a solvent-resistant microfluidic mixing device to produce discrete SVA gradients in solvent composition and/or total solvent concentration. Using this device, we identified solvent composition dependent morphology transformations in poly(styrene-b-isoprene-b-styrene) films.

Investigation of thermally responsive block copolymer thin film morphologies using gradients.

We report the use of a gradient library approach to characterize the structure and behavior of thin films of a thermally responsive block copolymer (BCP), poly(styrene-b-tert-butyl acrylate) (PS-b-PtBA), which exhibits chemical deprotection and morphological changes above a thermal threshold. Continuous gradients in temperature and film thickness, as well as discrete substrate chemistry conditions, were used to examine trends in deprotection, nanoscale morphology, and chemical structure. Thermal gradient annealing permitted the extraction of transformation rate constants (k(t)) for the completion of thermal deprotection and rearrangement of the film morphology from a single BCP library on hydroxyl and alkyl surfaces, respectively.

Generation of monolayer gradients in surface energy and surface chemistry for block copolymer thin film studies.

We utilize a vapor deposition setup and cross-diffusion of functionalized chlorosilanes under dynamic vacuum to generate a nearly linear gradient in surface energy and composition on a silicon substrate. The gradient can be tuned by manipulating chlorosilane reservoir sizes and positions, and the gradient profile is independent of time as long as maximum coverage of the substrate is achieved. Our method is readily amenable to the creation of gradients on other substrate surfaces, due to the use of vapor deposition, and with other functionalities, due to our use of functionalized chlorosilanes.