Hwan Chul Jeon

Controlled Origami Folding of Hydrogel Bilayers with Sustained Reversibility for Robust Microcarriers

Microencapsulation and controlled release have long been studied because of the high demand for practical delivery systems in the pharmaceutics and cosmetics fields. Multiphase emulsion drops have provided efficient templates for microcapsules, and various feasible methods have been developed for controlled release. However, the emulsion-based approach has limitations for the in situ control of membrane permeability. Micro-origami has emerged as one of the most promising alternative approaches for producing tunable microcapsules with the potential to be applied, for example as drug carriers, actuators, microcontainers, and microrobots. Inspired by living organisms in nature such as the ice plant and Venus flytrap, two different micro-origami approaches have been employed to make various microstructures. One approach uses solid patches connected by active hinge materials. Typical examples use various metal– metal, metal–polymer, and polymer–polymer combinations. The patch and hinge system has enabled the capture, release, and gripping of target materials, showing the feasibility of micro-origami structures. However, the microcapsule is limited to polyhedral shapes in this approach, and complete sealing of the gaps between patches requires exquisite control of the folding angles. Moreover, the delicate and complex fabrication processes make practical applications difficult. The second approach uses a bilayer structure composed of two different materials. For example, a metal– polymer bilayer can show bending/unbending when the polymeric active layer suffers significant volume change, but the metal layer remains unchanged. 13] Polymer materials have been employed in both layers to make biocompatible microcapsules. 15] However, complete sealing of the gaps in the bilayer contact regions remains an important, yet unmet, need. In addition, a simple and effective method for the fabrication of practical microcapsules has not yet been developed, and remains highly desirable. This is the main thrust of the present study. Herein, we report the use of biocompatible bilayer structures for the fabrication of tunable microcapsules based on micro-origami. Monodisperse bilayer microstructures were prepared using a facile photolithographic procedure, without employing photomask alignment. In addition, highly flexible hydrogels were selected as both active and passive layers, facilitating tight contact between patches. The bilayer structure therefore enabled in situ encapsulation, through a reversible transformation to microcapsules with a closed compartment. The resultant microcapsules showed negligible leakage of encapsulants and triggered release of the encapsulants could be achieved simply by inducing the unfolding of the hydrogel bilayer. The essential strategy of our approach relies on the anisotropic volume change of a hydrogel bilayer. As shown in Scheme 1a, the active hydrogel layer shows significant volume expansion under external stimuli by swelling, whereas the passive hydrogel layer remains in a constant volume. Therefore, mechanical stress drives the bending of the bilayer, resulting in microcapsules with a closed compartment. The hydrogel swelling behavior is highly reversible, enabling repeated transformations. The hydrogel bilayer structure was prepared on a glass substrate, using photolithography with an amorphous silicon photomask, as shown in Scheme 1b. Here, we propose poly(2hydroxyethyl methacrylate-co-acrylic acid), p(HEMA-coAA), and poly(2-hydroxyethyl methacrylate), p(HEMA), as model components because they are widely used, FDAapproved (FDA = Food and Drug Administration) biocompatible materials. One monomer solution for p(HEMA-coAA) was infiltrated into the space between the photomask and a polydimethylsiloxane (PDMS) microchannel of 25 mm thickness; this monomer solution was then polymerized by UV irradiation through the photomask. The second monomer solution for p(HEMA) was infiltrated into the space between the same photomask and a PDMS microchannel 50 mm in thickness, after washing out the previously unpolymerized solution. Upon the second round of UV irradiation, bilayer structures consisting of a p(HEMA) layer on a p(HEMA-coAA) layer were formed; alignment of the photomask was unnecessary, because each layer was fabricated on the photomask. The resultant bilayer structures were released from the photomask through immersion in a pH 9 buffer solution. To exploit the structural transformation of the bilayer microparticles, we used two different shapes of microparticle: snowman-shaped and flower-shaped. The shape and dimensions of these microparticles were carefully determined to ensure a fully closed compartment in the swollen state; both the snowmanand flower-shaped microparticles were 50 mm [*] T. S. Shim, Dr. S.-H. Kim, Dr. C.-J. Heo, H. C. Jeon, Prof. S.-M. Yang National Creative Research Initiative Center for Integrated Optofluidic Systems and Department of Chemical and Biomolecular Engineering KAIST Daejeon, 305-701 (Korea) E-mail: smyang@kaist.ac.kr Homepage: http://msfl.kaist.ac.kr

Durable plasmonic cap arrays on flexible substrate with real-time optical tunability for high-fidelity SERS devices.

Active tunable plasmonic cap arrays were fabricated on a flexible stretchable substrate using a combination of colloidal lithography, lift-up soft lithography, and subsequent electrostatic assembly of gold nanoparticles. The arrangement of the plasmonic caps could be tuned under external strain to deform the substrate in reversible. Real-time variation in the arrangement could be used to tune the optical properties and the electromagnetic field enhancement, thereby a proving a promising mechanism for optimizing the SERS sensitivity.

Shape control of Ag nanostructures for practical SERS substrates.

Large-area, highly ordered, Ag-nanostructured arrays with various geometrical features were prepared for use as surface-enhanced Raman scattering (SERS)-active substrates by the self-assembly of inorganic particles on an SU-8 surface, followed by particle embedding and Ag vapor deposition. By adjusting the embedding time of the inorganic particles, the size of the Ag nanogap between the geometrically separated hole arrays and bowl-shaped arrays could be controlled in the range of 60 nm to 190 nm. More importantly, the SU-8 surface was covered with hexagonally ordered nanopillars, which were formed as a result of isotropic dry etching of the interstices, leading to triangular-shaped Ag plates on nanopillar arrays after Ag vapor deposition. The size and sharpness of the triangular Ag nanoplates and nanoscale roughness of the bottom surface were adjusted by controlling the etching time. The potential of the various Ag nanostructures for use as practical SERS substrates was verified by the detection of a low concentration of benzenethiol. Finite-difference time-domain (FDTD) methodology was used to demonstrate the SERS-activities of these highly controllable substrates by calculating the electric field intensity distribution on the metallic nanostructures. These substrates, with high sensitivity and simple shape-controllability, provide a practical SERS-based sensing platform.

3D Hierarchical Architectures Prepared by Single Exposure Through a Highly Durable Colloidal Phase Mask

Three-dimensional hierarchical architectures are fabricated using a simple, cost-effective, durable colloidal phase mask containing a colloidal monolayer embedded in a flexible polydimethylsiloxane (PDMS) membrane. These structures give rise to a photonic bandgap that can be tuned over a wide spectral range from the visible to the near-infrared regions.

Anisotropic wetting and superhydrophobicity on holographically featured 3D nanostructured surfaces

Holographically featured SU-8 polymer surfaces exhibited anisotropic wetting by water droplets, due to liquid pinning at the edges of the top rods in 3D woodpile structures. Square nanopillar array surfaces (tip size, 30 nm) resulting from SF6 plasma treatment showed ultrahydrophobicity, with advancing and receding contact angles of 170°.

Unconventional methods for fabricating nanostructures toward high-fidelity sensors

Plasmonic materials fabricated from precisely controlled metal nanostructures provide promising platforms for developing high-sensitivity sensing devices, such as pH sensors, organic vapor sensors, and other chemical sensors. Over the past several decades, a number of unconventional methods for preparing localized surface plasmon resonance (LSPR)-based metal nanostructures have been developed in an effort to design high-fidelity sensors. Recent advances in plasmon-based optical sensors based on plasmonic nanostructures have made remarkable progress in overcoming the constraints of conventional optical sensors in terms of providing tunability, improved sensitivity, and good fidelity. In this review, we highlight the current state of the art in this field with an emphasis on the fabrication of plasmonic materials using unconventional methods and their demonstrated applications. We describe the remarkable achievements that have improved the performance of sensors for certain sensing systems. Finally, we present a perspective on the future development of LSPR sensors, including a discussion of the advances needed to elevate sensor performance to a level required for practical devices in the laboratory and in medical diagnostics.

Fabrication of 3D ZnO hollow shell structures by prism holographic lithography and atomic layer deposition

Highly uniform 3D ZnO hollow shell structures were prepared by combining prism holographic lithography (PHL) and atomic layer deposition (ALD). As a dense ZnO film was obtained by using the ALD process, no volume shrinkage occurred during the subsequent calcination to remove the sacrificial polymer template. No volume shrinkage during heat treatment is crucial for achieving excellent optical properties and mechanical stability of inverse photonic crystals (PCs).

Nanoarchitectures with controllable anisotropic features in structures and properties from simple and robust holographic lithography.

Anisotropic nanostructures with precise orientations or sharp corners display unique properties that may be useful in a variety of applications; however, precise control over the anisotropy of geometric features, using a simple and reproducible large-area fabrication technique, remains a challenge. Here, we report the fabrication of highly uniform polymeric and metallic nanostructure arrays prepared using prism holographic lithography (HL) in such a way that the isotropy that can be readily and continuously tuned. The prism position on the sample stage was laterally translated to vary the relative intensities of the four split beams, thereby tuning the isotropy of the resulting polymer nanostructures through the following shapes: circular nanoholes, elliptical nanoholes, and zigzag-shaped nanoarrays. Corresponding large-area, defect-free anisotropic metallic nanostructures could then be fabricated using an HL-featured porous polymer structure as a milling mask. Removal of the polymer mask left zigzag-shaped metallic nanostructure arrays in which nanogaps separated adjacent sharp edges. These structures displayed two distinct optical properties, depending on the direction along which the excitation beam was polarized (longitudinal and transverse modes) incident on the array. Furthermore, bidirectional anisotropic wetting was observed on the anisotropic polymer nanowall array surface.

Hierarchical nanostructures created by interference of high-order diffraction beams

We report a novel method to create 2D hierarchical nanopatterns with high structural complexity using phase-shift lithography. With phase masks with large lattice periodicities relative to the wavelength of the light source, several different diffraction beams are generated from a single grating, which then interfere to form a highly complex 3D intensity profile at the Fresnel region. We transfer the horizontal slice of the intensity profile into the thin film of negative photoresist, making 2D nanostructures. Because the diffraction order determines a length scale of intensity variation in a horizontal surface, interference of several different diffraction orders leads to the formation of complex and hierarchical nanopatterns, which are difficult to create with conventional phase-shift lithography. In addition, as the 2D profile is modulated along the light propagation direction, a variety of complex nanopatterns can be fabricated from a single phase mask by adjusting the distance between the diffraction grating and photoresist film. A full 3D intensity profile formed by interference is calculated using the finite-difference time domain (FDTD) method, which enables us to anticipate the shape and morphology of the resulting 2D nanostructures.

Fabrication of Au-Decorated 3D ZnO Nanostructures as Recyclable SERS Substrates

Highly roughened Au-decorated 3D ZnO nano-structures were prepared using a combination of prism holographic lithography and atomic layer deposition techniques. Prism holographic lithography is a simple and rapid method for fabricating ordered 3D nanostructures using the optical interference effects of multiple beams derived from a specially designed prism. Highly ordered reproducible surface-enhanced Raman scattering (SERS) substrates are needed for the reliable calibration of target analyte concentrations. A high density of Au nanoparticles separated by nanoscale gaps was generated on the Au-coated ZnO inverse structures. The nanogaps may function as strong hot spots for highly sensitive SERS-based chemical/biological sensors. The optimized SERS intensity from the prepared Au-coated 3D ZnO inverse structures was 20 times the intensity obtained from an Au-coated flat glass control substrate. The surfaces could be reused after the photocatalytic degradation and removal of adsorbates in the presence of ZnO. The Au-coated 3D ZnO structures described here offer an alternative to traditional single-use SERS substrates.