Marvin Y. Paik

Control of Self-Assembly of Lithographically Patternable Block Copolymer Films

Poly(alpha-methylstyrene)-block-poly(4-hydroxystyrene) acts as both a lithographic deep UV photoresist and a self-assembling material, making it ideal for patterning simultaneously by both top-down and bottom-up fabrication methods. Solvent vapor annealing improves the quality of the self-assembled patterns in this material without compromising its ability to function as a photoresist. The choice of solvent used for annealing allows for control of the self-assembled pattern morphology. Annealing in a nonselective solvent (tetrahydrofuran) results in parallel orientation of cylindrical domains, while a selective solvent (acetone) leads to formation of a trapped spherical morphology. Finally, we have self-assembled both cylindrical and spherical phases within lithographically patterned features, demonstrating the ability to precisely control ordering. Observing the time evolution of switching from cylindrical to spherical morphology within these features provides clues to the mechanism of ordering by selective solvent.

Amphiphilic Surface Active Triblock Copolymers with Mixed Hydrophobic and Hydrophilic Side Chains for Tuned Marine Fouling-Release Properties

Two series of amphiphilic triblock surface active block copolymers (SABCs) were prepared through chemical modification of two polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymer precursors. The methyl ether of poly(ethylene glycol) [M(n) approximately 550 g/mol (PEG550)] and a semifluorinated alcohol (CF(3)(CF(2))(9)(CH(2))(10)OH) [F10H10] were attached at different molar ratios to impart both hydrophobic and hydrophilic groups to the isoprene segment. Coatings on glass slides consisting of a thin layer of the amphiphilic SABC deposited on a thicker layer of an ABA polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thermoplastic elastomer were prepared for biofouling assays with algae. Dynamic water contact angle analysis, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) measurements were utilized to characterize the surfaces. Clear differences in surface structure were realized as the composition of attached side chains was varied. In biofouling assays, the settlement (attachment) of zoospores of the green alga Ulva was higher for surfaces incorporating a large proportion of the hydrophobic F10H10 side chains, while surfaces with a large proportion of the PEG550 side chains inhibited settlement. The trend in attachment strength of sporelings (young plants) of Ulva did not show such an obvious pattern. However, amphiphilic SABCs incorporating a mixture of PEG550 and F10H10 side chains performed the best. The number of cells of the diatom Navicula attached after exposure to flow decreased as the content of PEG550 to F10H10 side chains increased.

Direct Patterning of Intrinsically Electron Beam Sensitive Polymer Brushes

The fabrication of patterned polymer brushes has attracted considerable attention as these structures can be exploited in devices on the nano- and microscale. Patterning of polymer brushes is typically a complex, multistep process. We report the direct patterning of poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(isobutyl methacrylate) (PIBMA), poly(neopentyl methacrylate) (PNPMA), and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) brushes in a single step by electron beam (e-beam) lithography, to obtain nanopatterned polymer brush surfaces. PMMA, PHEMA, PIBMA, PNPMA, and PTFEMA brushes were grown on silicon substrates via surface-initiated atom transfer radical polymerization. Surface analysis techniques including ellipsometry, contact angle goniometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the thickness, hydrophilicity, roughness, and chemical composition of the polymer brushes. Tapping-mode AFM imaging confirmed the successful electron beam patterning of these brushes. Using this direct patterning method, highly resolved nanostructured polymer brush patterns down to 50 nm lines were obtained. This direct patterning of brushes eliminates the need for complex lithographic schemes. The sensitivity of these polymer brushes toward direct patterning with e-beam was studied and compared. The sensitivity curves indicate that the structure of the e-beam degradable methacrylate polymer has a significant effect on the sensitivity of the polymer brush toward e-beam patterning. In particular, the effect of the chemical functionality at the beta-position to the carbonyl group on the polymer brush sensitivity toward direct patterning was studied using groups of varying size and polarity.

Protein adsorption resistance of anti-biofouling block copolymers containing amphiphilic side chains

Surface active block copolymers (SABCs) with amphiphilic side chains containing ethoxylated fluoroalkyl groups have previously demonstrated advantageous properties with regard to marine fouling resistance and release. While it was previously postulated that the ability of the block copolymer surface to undergo an environment-dependent transformation in surface structure aided this behaviour, protein adsorption characteristics of the surface were never explored. This study aims to expand our knowledge of protein interaction with the amphiphilic surface active block copolymer in an aqueous environment through experiments with bovine serum albumin (BSA), a widely utilized test protein. Fluorescence microscopy analysis using BSA labelled with fluorescein isothiocyanate (BSA–FITC) was performed on a SABC test surface to establish the polymers protein adsorption resistance. Additionally, atomic force microscopy (AFM) based chemical force microscopy (CFM) was utilized to examine the force of adhesion of an AFM tip functionalized with strands of BSA protein with the SABC. No measurable force of adhesion was detected for 58% of the measurements of adhesion force taken for a BSA coated AFM tip interacting with the surface of the amphiphilic SABC in a PBS buffer. Furthermore, no measurements of force of adhesion were made in excess of 0.15 nN. This was in contrast to the non-zero mean adhesion force seen for several control surfaces in PBS buffer.

Patterning of polymer brushes. A direct approach to complex, sub-surface structures.

We report a unique method to directly fabricate complex polymer brush structures with nanometer scale features by means of electron beam lithography. Polymer brushes for direct patterning were grown from surface-anchored initiator sites using atom transfer radical polymerization. Selected monomers (poly(2-hydroxyethyl methacrylate) and poly(methyl methacrylate)) were used based on their ability to readily scission when exposed to radiation. Single step direct patterning of polymer brushes is attractive as this eliminates many process steps, reducing the possibility of contamination and possibly improving resolution. In addition, we report a method to form subsurface polymer brush channels with nanometer-scale features. With the chains tethered to a surface, a diblock copolymer brush with a negative tone upper layer (polystyrene) and a positive tone under layer (poly(methyl methacrylate)) or (poly(2-hydroxyethyl methacrylate) were patterned to create channels. In the work presented, the direct electron beam patterning behavior of the brushes was studied and fabrication of nanochannels was demonstrated. Imaging of the nanopatterned surfaces was carried out using atomic force microscopy and fluorescence microscopy.

Antimicrobial Behavior of Semifluorinated-Quaternized Triblock Copolymers against Airborne and Marine Microorganisms

Semifluorinated-quaternized triblock copolymers (SQTCs) were synthesized by chemical modification of polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymers. Surface characterization of the polymers was performed by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) analysis. The surface of the SQTC showed very high antibacterial activity against the airborne bacterium Staphylococcus aureus with >99 % inhibition of growth. In contrast in marine fouling assays, zoospores of the green alga Ulva settled on the SQTC, which can be attributed to the positively charged surface. The adhesion strength of sporelings (young plants) of Ulva and Navicula diatoms (a unicellular alga) was high. The SQTC did not show marked algicidal activity.

Development of a Directly Patterned Low-Surface-Energy Polymer Brush in Supercritical Carbon Dioxide

Carbon dioxide (CO2) is a sustainable solvent because it is nonflammable, exhibits a relatively low toxicity, and is naturally abundant. As a selective, nonpolar solvent, supercritical CO2 (scCO2) is an ideal fit for the development of low-surface-energy polymers. The development of directly patterned poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) brushes in scCO2 was investigated. PTFEMA, in particular, was selected over other fluorinated polymers because of its very high electron-beam (e-beam) sensitivity. PTFEMA brushes were grown on silicon substrates via controlled surface-initiated atom-transfer radical polymerization of TFEMA. Surface analysis techniques including ellipsometry, contact-angle goniometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy were used to characterize the thickness, hydrophilicity, roughness, and chemical composition of the polymer brushes. PTFEMA brushes were directly patterned in a single step using e-beam lithography and were processed in an environmentally benign scCO2 solvent. Tapping-mode AFM imaging confirmed the successful e-beam patterning and development of these brushes. The sensitivity of PTFEMA brushes toward direct patterning with the e-beam, followed by scCO2 development, was studied and compared to development in tetrahydrofuran solvent. Using this direct-patterning method, followed by dry development in scCO2, highly resolved nanostructured polymer brush lines down to 78 nm could be prepared. This method can be generalized to prepare fluorinated low-surface-energy polymer brush surfaces in a single step for various applications.

New self-assembly strategies for next-generation lithography

Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.