Uniform Microgels Containing Agglomerates of Silver Nanocubes for Molecular Size-Selectivity and High SERS Activity.

Surface-enhanced Raman scattering (SERS) is a promising technique for molecular analysis as the molecular fingerprints (Raman spectra) are amplified to detectable levels compared with common spectroscopy. Metal nanostructures localize electromagnetic field on their surfaces, which can lead to dramatic increase of Raman intensity of molecules adsorbed. However, the metal surfaces are prone to contamination, thereby requiring pretreatment of samples to remove adhesive molecules. To avoid the pretreatment and potentially achieve point-of-care (POC) analysis, we have developed SERS-active microgels using the droplet-microfluidic system. As the microgels are composed of water-swollen network with consistent mesh size, they selectively allow diffusion of molecules smaller than the mesh, thereby excluding large adhesives. To render the microgels highly SERS-active, we destabilize silver nanocubes to form agglomerates, which are embedded in the matrix of microgels. The nanogaps in the agglomerates provide high sensitivity in Raman measurement and size-selective permeability of the microgel matrix obviates the pretreatment of samples. To validate the functions, we demonstrate the direct detection of Aspirin dissolved in whole blood without any pretreatment.

Microfluidic Production of Semipermeable Microcapsules by Polymerization-Induced Phase Separation.

Semipermeable microcapsules are appealing for controlled release of drugs, study of cell-to-cell communication, and isolation of enzymes or artificial catalysts. Here, we report a microfluidic strategy for creating monodisperse microcapsules with size-selective permeability using polymerization-induced phase separation. Monodisperse water-in-oil-in-water (W/O/W) double-emulsion drops, whose ultrathin middle layer is composed of photocurable resin and inert oil, are generated in a capillary microfluidic device, and irradiated by UV light. Upon UV illumination, the monomers are photopolymerized, which leads to phase separation between the polymerized resin and the oil within the ultrathin shell. Subsequent dissolution of the oil leaves behind regular pores in the polymerized membrane that interconnect the interior and exterior of the microcapsules, thereby providing size-selective permeability. The degree of phase separation can be further tuned by adjusting the fraction of oil in the shell or the affinity of the oil to the monomers, thereby enabling the control of the cutoff value of permeation. High mechanical stability and chemical resistance of the microcapsules, as well as controllable permeability and high encapsulation efficiency, will provide new opportunity in a wide range of applications.

Droplet microfluidics for producing functional microparticles.

Isotropic microparticles prepared from a suspension that undergoes polymerization have long been used for a variety of applications. Bulk emulsification procedures produce polydisperse emulsion droplets that are transformed into spherical microparticles through chemical or physical consolidation. Recent advances in droplet microfluidics have enabled the production of monodisperse emulsions that yield highly uniform microparticles, albeit only on a drop-by-drop basis. In addition, microfluidic devices have provided a variety of means for particle functionalization through shaping, compartmentalizing, and microstructuring. These functionalized particles have significant potential for practical applications as a new class of colloidal materials. This feature article describes the current state of the art in the microfluidic-based synthesis of monodisperse functional microparticles. The three main sections of this feature article discuss the formation of isotropic microparticles, engineered microparticles, and hybrid microparticles. The complexities of the shape, compartment, and microstructure of these microparticles increase systematically from the isotropic to the hybrid types. Each section discusses the key idea underlying the design of the particles, their functionalities, and their applications. Finally, we outline the current limitations and future perspectives on microfluidic techniques used to produce microparticles.

Fabrication of three-dimensional nanostructured titania materials by prism holographic lithography and the sol-gel reaction.

We present a simple, easy method for fabricating high-quality titania inverted replicas of 3D holographically featured structures. A combination of single-prism holographic lithography and sol-gel chemistry was used to prepare 3D titania inverse structures with flat and completely open surfaces without the use of additional postprocessing steps, such as reactive ion etching, ion-beam milling, and/or polishing steps. A hydrophobic, stable liquid titania precursor facilitated the complete infiltration of the precursor into the hydrophobic 3D SU-8 polymer template, which produced very uniform high-quality titania inverse structures. Although the degree of film shrinkage during the calcination process was large (∼34%), the optical strength of the 3D titania inverse photonic crystals doubled because of the high-refractive-index contrast. Compared to titania inverse opal structures, the filling fraction (∼27%) of titania materials has been doubled. This is the first work to fabricate titania inverse photonic crystals with a high filling fraction by utilizing prism holographic lithography and the sol-gel chemistry reaction of a stable titania precursor. The X-ray diffraction patterns indicated the presence of a crystalline anatase or rutile phase depending on the calcination temperature.

Controlled Insertion of Planar Defect in Inverse Opals for Anticounterfeiting Applications.

Inverse opals have been used for structural coloration and photonic applications owing to their photonic bandgap properties. When the photonic structures contain planar defects, they provide defect modes, which are useful for lasing, sensing, and waveguiding. However, it remains a challenge to insert a planar defect into inverse opals in a reproducible manner. Here, we report a new method for producing planar-defect-inserted inverse opals using sequential capillary wetting of colloidal crystals and creating micropatterns through photolithography. Three cycles of deposition and thermal embedding of colloidal crystals into the underlying film of negative photoresist were performed. In the three cycles, opal, particle monolayer, and opal were sequentially employed, which yielded the monolayer-templated planar defect sandwiched by two inverse opals after particle removal. The planar defect provided a passband whose wavelength can be controlled by adjusting the diameter of particles for the defect layer. Moreover, the defect-inserted inverse opals can be micropatterned by photolithography as the negative photoresist is used as a matrix. The resulting micropatterns deliver a unique spectral code featured by a combination of stop band and defect mode and a graphical code dictated by photolithography, being useful for anticounterfeiting applications.

Droplet-Guiding Superhydrophobic Arrays of Plasmonic Microposts for Molecular Concentration and Detection.

Droplet-guiding superhydrophobic SERS substrates are created by a combinatorial lithographic technique. Photolithography defines the pattern of a micropillar array with a radial density gradient, whereas colloidal lithography features a nanotip array on the top surface of each micropillar. The nanotip array renders the surface superhydrophobic, and the pattern of micropillars endows the radial gradient of the contact angle, enabling the spontaneous droplet migration toward the center of the pattern. Water droplets containing target molecules are guided to the center, and the molecules dissolved in the droplets are concentrated at the surface of the central micropillar during droplet evaporation. Therefore, the molecules can be analyzed at the predefined position by Raman spectra without scanning the entire substrate. At the same time, the SERS-active nanotip array provides high sensitivity of Raman measurement.

Nanostructured plasmonic substrates for use as SERS sensors.

Plasmonic nanostructures strongly localize electric fields on their surfaces via the collective oscillations of conducting electrons under stimulation by incident light at a certain wavelength. Molecules adsorbed onto the surfaces of plasmonic structures experience a strongly enhanced electric field due to the localized surface plasmon resonance (LSPR), which amplifies the Raman scattering signal obtained from these adsorbed molecules. This phenomenon is referred to as surface-enhanced Raman scattering (SERS). Because Raman spectra serve as molecular fingerprints, SERS has been intensively studied for its ability to facilely detect molecules and provide a chemical analysis of a solution. Further enhancements in the Raman intensity and therefore higher sensitivity in SERS-based molecular analysis have been achieved by designing plasmonic nanostructures with a controlled size, shape, composition, and arrangement. This review paper focuses on the current state of the art in the fabrication of SERS-active substrates and their use as chemical and biosensors. Starting with a brief description of the basic principles underlying LSPR and SERS, we discuss three distinct nanofabrication methods, including the bottom-up assembly of nanoparticles, top-down nanolithography, and lithography-free random nanoarray formation. Finally, typical applications of SERS-based sensors are discussed, along with their perspectives and challenges.

Large-Area Accurate Position Registry of Microparticles on Flexible, Stretchable Substrates Using Elastomer Templates.

This work introduces a robust means for excellent position registry of microparticles via a forced assembly technique on flexible or stretchable substrates. It is based on the dry powder rubbing process which allows assembly of a microparticle monolayer in a short time without requiring any solvent or thermal treatment. Elastic physical templates are used as substrates for the forced assembly in this study. Since the elastic templates can reduce the stress accumulation between the closely packed particles, they can minimize the defect formation in the particle assembly in large areas. The method can be used with powders comprising irregularly shaped particles with a relatively large size distribution that cannot be periodically ordered by conventional self-assembly. Furthermore, a non-closely packed particle array can be fabricated readily in large area, which is highly desirable for practical uses of the particle monolayers. The particle monolayers formed on the elastomer templates can be transferred to surfaces coated with thermoplastic block copolymers. Once transferred, the particle monolayers are flexible and stretchable over their entire surface. This work uses the particle monolayers on a large-area flexible substrate as photomasks to produce various photoresist patterns.

3D Hybrid Plasmonic Nanomaterials for Highly Efficient Optical Absorbers and Sensors.

3D hybrid plasmonic nanomaterials are composed of 3D-stacked Ag nanowires and nanoparticles separated by a nanoscale-thick alumina interlayer. The 3D hybrid plasmonic nanostructures exhibit strong plasmonic coupling between the ultrahigh populations of plasmonic nanomaterials, overcoming the physical limitation of inefficient plasmonic coupling of the Ag nanowire stacks.

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.

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.

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.