Pitch-tunable size reduction patterning with a temperature-memory polymer.

A scalable and pitch-tunable size reduction patterning method is introduced by exploiting the temperature memory effect of shape memory polymer and replica molding of UV-curable materials.

A nontransferring dry adhesive with hierarchical polymer nanohairs.

We present a simple yet robust method for fabricating angled, hierarchically patterned high-aspect-ratio polymer nanohairs to generate directionally sensitive dry adhesives. The slanted polymeric nanostructures were molded from an etched polySi substrate containing slanted nanoholes. An angled etching technique was developed to fabricate slanted nanoholes with flat tips by inserting an etch-stop layer of silicon dioxide. This unique etching method was equipped with a Faraday cage system to control the ion-incident angles in the conventional plasma etching system. The polymeric nanohairs were fabricated with tailored leaning angles, sizes, tip shapes, and hierarchical structures. As a result of controlled leaning angle and bulged flat top of the nanohairs, the replicated, slanted nanohairs showed excellent directional adhesion, exhibiting strong shear attachment (approximately 26 N/cm(2) in maximum) in the angled direction and easy detachment (approximately 2.2 N/cm(2)) in the opposite direction, with a hysteresis value of approximately 10. In addition to single scale nanohairs, monolithic, micro-nanoscale combined hierarchical hairs were also fabricated by using a 2-step UV-assisted molding technique. These hierarchical nanoscale patterns maintained their adhesive force even on a rough surface (roughness <20 microm) because of an increase in the contact area by the enhanced height of hierarchy, whereas simple nanohairs lost their adhesion strength. To demonstrate the potential applications of the adhesive patch, the dry adhesive was used to transport a large-area glass (47.5 x 37.5 cm(2), second-generation TFT-LCD glass), which could replace the current electrostatic transport/holding system with further optimization.

Anisotropic adhesion properties of triangular-tip-shaped micropillars.

Directional dry adhesive microstructures consisting of high-density triangular-tip-shaped micropillars are described. The wide-tip structures allow for unique directional shear adhesion properties with respect to the peeling direction, along with relatively high normal adhesion.

Mold design rules for residual layer-free patterning in thermal imprint lithography.

We present the mold design rules for assuring residual layer-free patterning in thermal imprint processes. Using simple relations for mass balance, structural stability, and work of adhesion, we derive the conditions with respect to the given single or multigeometrical feature of the mold, which are compared with simple thermal imprint experiments using soft imprint molds. Our analysis could serve as a guideline for designing the optimum mold geometry and selecting mold material in residual layer-free thermal imprint processes.

Stabilization of ion concentration polarization using a heterogeneous nanoporous junction.

We demonstrate a recycled ion-flux through heterogeneous nanoporous junctions, which induce stable ion concentration polarization with an electric field. The nanoporous junctions are based on integration of ionic hydrogels whose surfaces are negatively or positively charged for cationic or anionic selectivity, respectively. Such heterogeneous junctions can be matched up in a way to achieve continuous ion-flux operation for stable concentration gradient or ionic conductance. Furthermore, the combined junctions can be used to accumulate ions on a specific region of the device.

Use of directly molded poly(methyl methacrylate) channels for microfluidic applications.

A direct molding method for creating a homogeneous, polymer microfluidic channel is presented. By utilizing capillary rise and subsequent absorption of poly(methyl methacrylate) (PMMA) solution into a solvent-permeable poly(dimethyl siloxane) (PDMS) mold, various circular or elliptic polymer microchannels were fabricated without channel bonding and additional surface modification processes. In addition, the channel diameter was tunable from several micrometres to several hundreds of micrometres by controlling concentration and initial amount of polymer solution for a given PDMS mold geometry. The molded PMMA channels were used for two applications: blocking absorption of Rhodamine B dye and constructing artificial endothelial cell-cultured capillaries. It was observed that the molded PMMA channels effectively prevented absorption and diffusion of Rhodamine molecules over 5 h time span, demonstrating approximately 40 times higher blocking efficiency as compared to porous PDMS channels. Also, calf pulmonary artery endothelial cells (CPAEs) adhered, spread, and proliferated uniformly within the molded microchannels to form near confluency within 3 days and remained viable at day 6 without notable cell death, suggesting high biocompatibility and possibility for emulating in vivo-like three-dimensional architecture of blood vessels.

Adhesion assays of endothelial cells on nanopatterned surfaces within a microfluidic channel.

We present a simple analytical method to measure adhesion of human umbilical vein endothelial cells (HUVECs) and calf pulmonary artery endothelial cells (CPAEs) using nanopatterned, biodegradable poly(lactic-co-glycolic acid) (PLGA) surfaces for potential applications to artificial tissue-engineered blood vessel. Various nanostructured PLGA surfaces (350 nm wide ridges/350 nm grooves, 350 nm ridges/700 nm grooves, 350 nm ridges/1750 nm grooves, 700 nm ridges/350 nm grooves, 1050 nm ridges/350 nm grooves, 1750 nm ridges/350 nm grooves) and flat (unpatterned) surfaces were fabricated on the bottom of polydimethylsiloxane (PDMS) microfluidic channel of 2 mm width and 60 microm height by using thermal imprinting and irreversible channel bonding. To measure adhesion strength of HUVECs and CPAEs, the cells were exposed to a range of shear stress (12, 40, and 80 dyn/cm(2)) within the channels for 20 min after a preculture for 3 days and the remaining cells were counted under each condition. The highest adhesion strength was found on the surface of 700 nm wide ridges, 350 nm wide grooves for both cell types. The enhanced adhesion on nanopatterned surfaces can be attributed to two aspects: (i) contact guidance along the line direction and (ii) clustered focal adhesions. In particular, the contact guidance induced cell alignment along the line directions, which in turn lowers wall shear stress applied to the cell surface, as supported by a simple hydrodynamic model based on cell morphology.

Stretchable, adhesion-tunable dry adhesive by surface wrinkling.

We introduce a simple yet robust method of fabricating a stretchable, adhesion-tunable dry adhesive by combining replica molding and surface wrinkling. By utilizing a thin, wrinkled polydimethyl siloxane (PDMS) sheet with a thickness of 1 mm with built-in micropillars, active, dynamic control of normal and shear adhesion was achieved. Relatively strong normal (approximately 10.8 N/cm(2)) and shear adhesion (approximately 14.7 N/cm(2)) forces could be obtained for a fully extended (strained) PDMS sheet (prestrain of approximately 3%), whereas the forces could be rapidly reduced to nearly zero once the prestrain was released (prestrain of approximately 0.5%). Moreover, durability tests demonstrated that the adhesion strength in both the normal and shear directions was maintained over more than 100 cycles of attachment and detachment.

Face selection in one-step bending of Janus nanopillars.

We introduce a one-step procedure of bending nanopillars, which simply involves oblique metal deposition at a tilted angle of 45 degrees on the pillars by thermal evaporation. The face selection in the bending procedure was determined by the nature of residual stress generated in the metal film during evaporation. If the stress was tensile as with many metals (sigma(f) > 0), the Janus nanopillars were bent toward the metal face; if the residual stress was compressive as in the case of Al (sigma(f) < 0), they were bent toward the polymer face. It has also been demonstrated that groups of Janus nanopillars could be bent in different directions on the same substrate with the aid of a shadow-mask deposition. The degree of bending increased with the decrease in pillar diameter in the range of 360-800 nm for a fixed height of 1 microm.

Fabrication of antireflection and antifogging polymer sheet by partial photopolymerization and dry etching.

We present a simple method to fabricate a polymer optical sheet with antireflection and antifogging properties. The method consists of two consecutive steps: photocross-linking of UV-curable polyurethane acrylate (PUA) resin and reactive ion etching (RIE). During photopolymerization, the cured PUA film is divided into two domains of randomly distributed macromers and oligomers due to a relatively short exposure time of 20 s at ambient conditions. Using the macromer domain as an etch-mask, dry etching was subsequently carried out to remove the oligomer domain, leaving behind a nanoturf surface with tunable roughness. UV-vis spectroscopy measurements demonstrate that transmittance of a nanoturf surface is enhanced up to 92.5% as compared to a flat PUA surface (89.5%). In addition, measurements of contact angle (CA) reveal that the etched surface shows superhydrophilicity with a CA as small as 5 degrees. To seek potential applications, I-V characteristics of a thin film organic solar cell were measured under various testing conditions. It is shown that the efficiency can be increased to 2.9% when a nanoturf film with the surface roughness of 34.73 nm is attached to indium tin oxide (ITO) glass. More importantly, the performance is maintained even in the presence of water owing to superhydrophilic nature of the film.

Step-and-repeat process for thermal nanoimprint lithography.

We present a step-and-repeat process for thermal nanoimprint lithography. For the selective heating and imprinting, a spin-coated polystyrene layer is exposed to infra-red rays from a halogen lamp (intensity approximately 500 W) with a metal-covered glass while pressed with a transparent polymer mold (Young's modulus approximately 300 MPa) under a pressure of approximately 4 bar for 60-120 s. During imprinting, the non-irradiated region is protected by a metal screen and a heat sink consisting of a copper block at the bottom which prevents the pattern collapse by lateral heat conduction from the irradiated region.

Measurement of pull-off force on imprinted nanopatterns in an inert liquid.

We report on the measurement of the pull-off force on nanoscale patterns that are formed by thermal nanoimprint lithography (t-NIL). Various patterns with feature sizes in the range of 50-900 nm were fabricated on silicon substrates using a rigiflex polymeric mold of ultraviolet curable polyurethane acrylate (PUA, Young's modulus approximately 1 GPa) or perfluoropolyether (PFPE, Young's modulus approximately 10.5 MPa) and a resist layer of polystyrene (PS) of three different molecular weights (M(w) = 18,100, 211,600 and 2043,000). The pull-off force was measured in non-polar, non-reactive perfluorodecalin (PFD) solvent between a sharp atomic force microscopy (AFM) tip and an imprinted pattern. Our experimental data demonstrated that the measured pull-off forces were in good agreement with a simple adhesion model based on Lifshitz theory. Also, the force on the pressed region (valley) is higher than that on the cavity region (hill), with the ratio (hill/valley) decreasing with the decrease of pattern size and the increase of molecular weight. The confinement effects were more pronounced for smaller patterns (<300 nm) and higher molecular weights (M(w) = 211,600 and 2043,000) presumably due to sluggish movement of polymer chains into nano-cavities. Finally, the experimental observations were compared with molecular dynamic simulations based on a simplified amorphous polyethylene model.

Nanoarrays of tethered lipid bilayer rafts on poly(vinyl alcohol) hydrogels.

Lipid rafts are cholesterol- and sphingolipid-rich domains that function as platforms for signal transduction and other cellular processes. Tethered lipid bilayers have been proposed as a promising model to describe the structure and function of cell membranes. We report a nano(submicro) array of tethered lipid bilayer raft membranes (tLBRMs) comprising a biosensing platform. Poly(vinyl alcohol) (PVA) hydrogel was directly patterned onto a solid substrate, using ultraviolet-nanoimprint lithography (UV-NIL), as an inert barrier to prevent biofouling. The robust structures of the nanopatterned PVA hydrogel were stable for up to three weeks in phosphate-buffered saline solution despite significant swelling (100% in height) by hydration. The PVA hydrogel strongly restricted the adhesion of vesicles, resulting in an array of highly selective hydrogel nanowells. tLBRMs were not formed by direct vesicle fusion, although raft vesicles containing poly(ethylene glycol) lipopolymer were selectively immobilized on gold substrates patterned with PVA hydrogel. The deposition of tLBRM nano(submicro) arrays was accomplished by a mixed, self-assembled monolayer-assisted vesicle fusion method. The monolayer was composed of a mixture of 2-mercaptoethanol and poly(ethylene glycol) lipopolymer, which promoted vesicle rupture. These results suggest that the fabrication of inert nanostructures and the site-selective modification of solid surfaces to induce vesicle rupture may be essential in the construction of tLBRM nano(submicro) arrays using stepwise self-assembly.

Multi-curvature liquid meniscus in a nanochannel: evidence of interplay between intermolecular and surface forces.

We examined the formation of a multiply curved meniscus inside rectangular nanochannels, whose width ranges from 50 to 800 nm at a constant height of 200 nm. When the channel width is smaller than approximately 400 nm under partial wetting conditions, a distinct multi-curvature meniscus was observed at the advancing front with an edge disjoined from the wall. In contrast, a typical pre-wetting film was observed at the front regardless of the channel size for complete wetting conditions. Our theoretical analysis demonstrated that the multi-curvature meniscus is generated from the increased contribution of an extra pressure due to intermolecular interactions near the wall. In particular, a plug-like meniscus profile was observed at the advancing liquid front for the 50 nm wide channel owing to an overlap between convex curvatures at the channel walls. Finally, we showed that the filling velocity of liquid can be decreased by decreasing the channel size due to the reduced wettability.

Effects of mold rising angle and polymer concentration in solvent-assisted molding.

We investigated the capillary rise of a thin polymer solution in a simple soft lithographic technique termed "solvent-assisted molding (SAMo)" by using various mold rising angles and polymer concentrations in a good solvent. For patterning and mold materials, poly(methyl methacrylate) (PMMA, M(w) = 120,000) in toluene and poly(dimethyl siloxane) (PDMS) were mostly used. It was found that the capillary rise takes place in two steps: (i) a low-viscosity polymer solution rapidly rises into the cavity (<10 s) with the aid of solvent wetting and (ii) continuous solvent absorption into the mold and evaporation into air. In addition, five distinct microstructures were observed by testing 24 different experimental combinations, which can be classified into completely molded (I), humped (II), completely molded but non-fully filled (III), partially filled (IV), and partially filled meniscal (V) microstructures.

On the role of oxygen in fabricating microfluidic channels with ultraviolet curable materials.

We present the effects of oxygen on the irreversible bonding of a microchannel using an ultraviolet (UV) curable material of polyurethane acrylate (PUA). Microchannels were fabricated by bonding a top layer with impressions of a microfluidic channel and a bottom layer consisting of a PUA coating on a glass or a polyethylene terephthalate (PET) film substrate. The resulting channel is a homogeneous conduit of the PUA material. To find optimal bonding conditions, the bottom layer was cured under different oxygen concentration and UV exposure time at a constant UV intensity (10 mW cm(-2)). Our experimental and theoretical studies revealed that the channel bonding is severely affected by the concentration of oxygen either in the form of trapped air or permeated air out of the channel. In addition, an optimal UV exposure time is needed to prevent clogging or non-bonding of the channel.

Direct UV-replica molding of biomimetic hierarchical structure for selective wetting.

describe a one-step UV-replica molding method for fabricating a biomimetic dual-scale hierarchical structure. The use of UV-curable, acrylate-functionalized perfluoropolyethers allows for a high fidelity replication of a low-energy surface with multiscale texture, thereby directly creating a superhydrophobic surface without any complicated processing. The superhydrophobic surface can simply be transformed selectively into a superhydrophilic surface by exposure to deep ultraviolet light. The prepared surface is inert to chemicals and solvents and maintains its wettability over a long period of time.

Room temperature detachment nanolithography using a rigiflex polymeric mold.

We report on detachment nanolithography of an organic thin film at room temperature mediated by ultraviolet (UV) exposure. A nanopatterned, UV curable polyurethane acrylate (PUA) mold was placed on a spin-coated organic film made of 4,4'-bis[N-1-napthyl-N-phenyl-amino]biphenyl (NPB) under a low pressure (1-2 bar). A higher work of adhesion at the organic/mold interface induced detachment of the contacting layer on silicon or gold substrate, resulting in well-defined nanopatterns without a residual layer. The detachment was highly improved by a short-term UV exposure, rendering the film surface free from contaminant hydrocarbons with a lower cohesive force, as confirmed by Fourier transform infrared (FTIR) spectroscopy and measurements of contact angle of water.

Label-free, microfluidic separation and enrichment of human breast cancer cells by adhesion difference.

A label-free microfluidic method for separation and enrichment of human breast cancer cells is presented using cell adhesion as a physical marker. To maximize the adhesion difference between normal epithelial and cancer cells, flat or nanostructured polymer surfaces (400 nm pillars, 400 nm perpendicular, or 400 nm parallel lines) were constructed on the bottom of polydimethylsiloxane (PDMS) microfluidic channels in a parallel fashion using a UV-assisted capillary moulding technique. The adhesion of human breast epithelial cells (MCF10A) and cancer cells (MCF7) on each channel was independently measured based on detachment assays where the adherent cells were counted with increasing flow rate after a pre-culture for a period of time (e.g., one, two, and four hours). It was found that MCF10A cells showed higher adhesion than MCF7 cells regardless of culture time and surface nanotopography at all flow rates, resulting in label-free separation and enrichment of cancer cells. For the cell types used in our study, an optimum separation was found for 2 hours pre-culture on the 400 nm perpendicular line pattern followed by flow-induced detachment at a flow rate of 200 microl min(-1). The fraction of MCF7 cells was increased from 0.36 +/- 0.04 to 0.83 +/- 0.04 under these optimized conditions.

Inorganic polymer photoresist for direct ceramic patterning by photolithography.

A novel negative, inorganic polymer photoresist was demonstrated to be suitable for simple and direct fabrication of tribological SiCN-based ceramic microstructures via UV photolithography and subsequent pyrolysis at 800 degrees C.