Close-packed Polystyrene Research Articles

Multiple Resonances Induced by Plasmonic Coupling between Gold Nanoparticle Trimers and Hexagonal Assembly of Gold-Coated Polystyrene Microspheres.

Optical properties of a gold nanoparticle trimer assembly coupled with gold-coated hexagonally close-packed polystyrene microspheres were investigated by linear and nonlinear spectroscopy. The observed reflection spectrum shows multiple peaks from the visible to near-infrared spectral regions. The spectroscopic properties were also examined by a finite-difference time-domain simulation. We found that the optical response of plasmons excited in the gold nanoparticle trimers was significantly modulated by strong coupling of the plasmons and the photonic mode induced in the gold-coated polystyrene assembly. Two-photon induced photoluminescence and Raman scattering from the sample were investigated, and both signals were significantly enhanced at the gold nanoparticle assembly. The simulations reveal that the electric fields can be enhanced site-selectively, not only at the interstitial sites in the nanoparticle assembly but also at the gaps between the particle and the gold film due to plasmonic interactions, by tuning the wavelength and are responsible for the strong optical responses.

A combined electrochemical route to fabricate large-area and free-standing inverse opaline film

A combined electrochemical route involving electrophoresis and electrodeposition is developed to fabricate a large-area unsupported nickel inverse opaline film with thickness less than 10μm. A vertical electrophoresis allows for the packing of 495nm polystyrene microspheres on an ITO-coated glass to form a colloidal crystal with significantly reduced defects. Subsequently, a nickel electrodeposition is employed to fill the interstitial voids among the close-packed polystyrene microspheres, followed by the removal of the colloidal template in a two-stage process, leaving a robust nickel skeleton with hexagonally arranged pores and interconnected pore channels. This nickel skeleton is then detached from the ITO-coated glass via a liquid nitrogen treatment, rendering a free-standing nickel inverse opaline film in 2×2cm2. Porometer measurements indicate a narrow pore size distribution consistent with images from scanning electron microscope. We determine that the intensity ratio of (111)/(100) diffraction peak is an indicator for the strength of the Ni inverse opals, and thus affects its structural integrity upon detachment from the ITO-coated glass.

Nanostructured SERS substrates produced by nanosphere lithography and plastic deformation through direct peel-off on soft matter

We present a novel fragmented-film surface-enhanced Raman scattering (SERS) substrate produced by nanosphere lithography and direct peel-off for SERS efficacy enhancement. The 2D hexagonally close-packed polystyrene nanospheres on the polydimethylsilozane (PDMS) substrate are covered with silver film and then directly peeled off using sticky tape. During the peel-off process, the pulling force induces the stretch and contraction of the PDMS substrate and causes fracture of the 2D triangular silver film. Under laser excitation, a stronger localized electric field is induced in the smaller cracks and enhances the SERS intensity. The origin of this SERS enhancement is confirmed by numerical simulation using the finite element method and substrate annealing to smoothen the cracks. For the case using nanospheres with a diameter of 740 nm, an enhancement factor 6.5 × 106 can be achieved. The proposed fragmented-film SERS substrate gains 1.8 and 2.6 times larger Raman intensity at the 1358 cm−1 SERS peak than those using pyramidal silver islands and silver nanoshell array. The proposed SERS substrate has the features of easy fabrication, low production cost, short fabrication time and high enhancement factor.

Wetting behavior on hexagonally close-packed polystyrene bead arrays with different topographies.

Herein, we investigated the wetting behavior of hexagonally close-packed polystyrene bead arrays with different bead diameters and surface flatness. The contact angle was found to be influenced by the surface roughness as well as the contact area of the polystyrene bead array with a water droplet.

Size-dependent filtration of nanoparticles on porous films composed by polystyrene microsphere monolayers and applications in site-selective deposition of nanoparticles

Composite films composed of polystyrene (PS) microsphere monolayers and gold (Au) and/or silver (Ag) nanoparticles (NPs) decorations were prepared by a novel size-dependent filtration effect on close-packed PS microsphere arrays. The uniform pores inlaid in the PS monolayer films acted as the transport tunnels for NPs. The steric restriction induced by the size of the pores was used as a main strategy to fabricate hybrid micro/nano films, which were composed of PS microspheres with inhomogeneous anisotropic decorations. The Au and Ag NPs were used as the building blocks to decorate the PS microspheres through a layer-by-layer self-assembly technique with the aid of polyelectrolyte coupling agents. Only the small particles which could pass through the micropores could reach to and deposit on the inner surfaces of the PS microsphere monolayer films. Large particles remained on the outside and could only deposit on the outer surfaces. Thus, the inhomogeneous anisotropic decoration was obtained. This study provides a novel strategy for fabricating anisotropic micro/nanostructures by the size-dependent filtration effect of NPs on porous films and has the potential in applications of anisotropic self-assembly, sensor, and surface modifications at nanoscale.

Enhanced light absorption of amorphous silicon thin film by substrate control and ion irradiation

Large-area periodically aligned silicon nanopillar (PASiNP) arrays were fabricated by magnetic sputtering with glancing angle deposition (GLAD) on substrates coated by a monolayer of close-packed polystyrene (PS) nanospheres. The structure of PASiNP arrays could be manipulated by changing the diameter of PS nanospheres. Enhanced light absorptance within a wavelength range from 300 to 1,000 nm was observed as the diameter of nanopillars and porosity of PASiNP arrays increased. Meanwhile, Xe ion irradiation with dose from 1 × 1014 to 50 × 1014 ions/cm2 was employed to modify the surface morphology and top structure of thin films, and the effect of the irradiation on the optical bandgap was discussed.PACS code81.15.Cd; 78.66.Jg; 61.80.Jh

A Novel Method of Fabricating, Adjusting, and Optimizing Polystyrene Colloidal Crystal Nonspherical Microparticles from Gas–Water Janus Droplets in a Double Coaxial Microfluidic Device

The optical properties of close-packed polystyrene colloidal crystal particles could be improved and controlled via adjusting their shape, by first forming colloidal suspension–gas Janus droplets with different structures in a double coaxial microfluidic device, and then solvent-extraction-derived self-assembly to form nonspherical microparticles with different shapes.

Fabrication of Wafer-Size Monolayer Close-Packed Colloidal Crystals via Slope Self-Assembly and Thermal Treatment

We developed a simple and general approach for constructing a wafer-scale monolayer, close-packed polystyrene (PS), and SiO2 sphere arrays, namely colloidal crystals, which have significant potential in various applications. The method combines slope self-assembly and thermal treatment to achieve large-area and high-quality colloidal crystal with a proper slant angle (θ) and latex concentration (volume fraction, φ). The dependence of the structures of colloidal crystals on a dispersion system was also investigated. Moreover, a theoretical analysis of the slope self-assembly method was proposed. In addition, we applied the method to assemble PS spheres on different kinds of substrates, which indicates that the method is a versatile and reliable way to fabricate monolayer colloidal crystals.

The subwavelength tuned magneto-optical Kerr effect in L10-FePt films with perpendicular magnetic anisotropy

For L10-FePt films with strong perpendicular anisotropy covered by arrays of hexagonal close-packed polystyrene spheres (PSSs), fine structures are observed in magneto-optical Kerr rotation spectra in the visible spectral range. The reflection minima are found to be located at the same wavelengths as the Kerr rotation peaks. The Kerr rotation enhancement is attributed to the excitation of both the surface plasmon polariton in the dielectric PSS/metal interface and the guide waves (guide mode) in the PSS array. The two-dimensional PSSs/SiO2/FePt system exhibiting a tunable magneto-optical Kerr effect and a high perpendicular magnetic anisotropy will be helpful for designing and fabricating magneto-optics devices.

Direct observation of the phonon dispersion of a three-dimensional solid/solid hypersonic colloidal crystal

We report on Brillouin measurements of the phonon dispersion relation of a three-dimensional hypersonic phononic crystal. The phononic crystal, comprised of close-packed polystyrene spheres embedded in a background matrix of solid polydimethylsiloxane, was fabricated using a self-assembly technique. The experimentally measured dispersion relation reveals the band folding effect and the formation of a band gap for longitudinal waves at the boundary of the Brillouin zone. Theoretical calculations, based on the finite element method and the finite-difference time-domain method, are employed to interpret experimentally observed phonon modes and provide insight on important features of the solid/solid hypersonic crystals.

Template method for the synthesis of a heterogeneous fenton catalyst based on the hierarchical zeolite FeZSM-5

Zeolite h-FeZSM-5 with a hierarchical micro/macropore system has been synthesized in the presence of a template based on the close-packed polystyrene (PS) spheres, and the conventional zeolite FeZSM-5 has been obtained in the absence of a PS template. The zeolites have been characterized by X-ray diffraction, scanning and high-resolution transmission electron microscopy, and N2 sorption. The macropore walls of the hierarchical zeolite consist of ZSM-5 nanocrystals and amorphous globules of silica. Compared to the conventional zeolite, the hierarchical one has a high BET and external surface areas of 245 and 472 m2/g, respectively, and a high pore volume of 0.6 cm3/g. The catalytic properties of the Fe-containing zeolites were studied in the H2O2 decomposition reaction in the absence and in the presence of EDTA ligands and in the oxidation of low- and high-molecular-weight organic compounds by hydrogen peroxide at 25°C. Hierarchical zeolite h-FeZSM-5 is highly efficient in the oxidation of large molecules.

Controlled Fabrication of Silicon Nanowires via Nanosphere Lithograph and Metal Assisted Chemical Etching

We investigated the controlled fabrication of uniform vertical aligned silicon nanowires with desired length, diameter and location by combining nanosphere lithograph and metal assisted chemical etching techniques. The close-packed polystyrene nanospheres array was obtained by self-assemble technique, followed by reactive ion etching to acquire a non-close-packed monolayer template. Subsequently, the template was used to create a metal film with nanoholes array, which enable the controlled fabrication of ordered silicon nanowires via metal assisted chemical etching technique. By adjusting the monolayer of polystyrene nanospheres and the conditions for the metal assisted chemical etching, we obtained uniform distributed silicon nanowires with desired morphology. The aspect ratio of the silicon nanowires can reach to about 86:1. Furthermore, we have obtained the double-layer silicon nanowires by slight modifying the process. The influences of various conditions during etching were also discussed for improving the controlled fabrication.

Asymmetric Free-Standing 2-D Photonic Crystal Films and Their Janus Particles

We report the fabrication of large area, thin asymmetric free-standing two-dimensional (2-D) photonic crystals. We fabricate large area 2-D close-packed monodisperse polystyrene (PS) particle monolayers at air/water interfaces by using our needle tip flow method. We then layer tetraethyl orthosilicate (TEOS) onto the 2-D array to form a thin TEOS layer on the 2-D particle array on water. The hemispheres of PS particles located within the TEOS phase swell such that the adjacent particle hemispheres fuse. After TEOS evaporation, we obtain a free-standing connected photonic crystal film of hemispheres that efficiently diffracts light. The other side of the photonic crystal film consists of a fused connecting thin, flat sheet. Reactive ion etching (RIE) of the asymmetric films forms unusual, rough particle 2-D arrays and 2-D flower-like arrays. Mechanical abrasion allows one to separate the resulting novel Janus particles.

Enhanced light extraction efficiency for glass scintillator coupled with two-dimensional photonic crystal structure

In order to improve the light extraction efficiency for Tb3+-doped glass scintillator, we propose an effective approach by incorporating a two-dimensional photonic crystal structure: a periodic array of hexagonally close-packed polystyrene nanosphere monolayer onto glass surface. The in-plane vector for the light suffering total internal reflection is changed into light cone resulting light emission out of glass. The optimized diameter of polystyrene nanosphere is 500nm and the maximum enhancement of extraction efficiency reaches 25%. The enhancement shows angular dependence from the far-filed distribution pattern.

Tunable Magneto-Optical Kerr Effect in Fe Films Underneath a Two-Dimensional Array of Polystyrene Spheres Covered by Au Nanocaps

For Fe layers covered by two-dimensional arrays of hexagonal close-packed polystyrene spheres which are hemispherically covered by Au films on the top, fine structures are observed in reflection, magneto-optical Kerr rotation and ellipticity spectra. The Kerr rotation achieves peaks or exhibits a narrow resonance-like spectral lineshape near the reflection minima, depending on the mechanism of the reflection dips. The Kerr rotation peaks and the resonance-like lineshape both are shifted with the sphere diameters. These phenomena can be attributed to the excitation of surface plasmon resonance and Fabry—Pérot modes.

Highly efficient construction of oriented sandwich structures for surface-enhanced Raman scattering

The purpose of this study is to solve the problem of low achievement in fabricating sandwich surface-enhanced Raman scattering (SERS) substrates. We demonstrated a highly efficient sandwich structure by the oriented assembly of metal nanoparticles (NPs) on a periodic hexagonal array of metal nanoprisms with 1,4-benzenedithiol (1,4-BDT) as linkers. The metal nanoprism array was prepared by vacuum deposition of metal on a close-packed polystyrene nanosphere pre-patterned substrate. The metal nanoprism array presents different surface properties from the pits left from the removal of polystyrene nanospheres, which causes linkers to selectively adsorb on the metal nanoprism array and sequentially leads to the oriented immobilization of the second-layer metal NPs, avoiding mismatched orientation. These sandwich SERS substrates were characterized by extinction spectroscopy and atomic force microscopy and their enhancement activity was evaluated under different excitation wavelengths. The sandwich structure greatly increases the achievement of ‘hot spots’ to almost 100% of all the metal nanoprisms and enables a large amplification of SERS signals by a factor of ten. This method has the advantages of simplicity, high efficiency, high throughput, controllability and high reproducibility. It has significance in both the study of SERS substrates and the development of plasmonic devices.

Surface modes enhanced magneto-optical Kerr effect in Fe films underneath two-dimensional array of polystyrene spheres

For bilayers consisting of 20 nm Fe film and top two-dimensional arrays of hexagonal close-packed polystyrene spheres, fine structures are observed in the reflection R and magneto-optical polar Kerr rotation θK spectra. The θK achieves narrow peaks or dips near R minima and are both shifted with the sphere diameter. All phenomena are attributed to the excited guided waves and surface plasmonic modes. The θK peaks and dips near the R minima can be mainly explained as a result of the pure optical constant effect.

Monolayer Polystyrene Micro-Spheres Array Master Derived by Spin-Coating Method for UV Nanoimprint

Polystyrene micro-spheres aqueous suspensions were obtained by an emulsifier-free polymerization method. Fourier transform infrared spectroscopy and laser particle size distribution were used to characterize the colloidal solutions. Results indicate that the polystyrene micro-spheres colloidal solution has a good dispersion and the micro-spheres have a uniform size and smooth surface. The as-prepared polystyrene micro-spheres colloidal solution was spun onto glass substrates and then the coated sample was heated at 70 degrees C for 1 h to form close-packed monolayer polystyrene microspheres arrays, which are used as a master. Scanning electron microscopy was used to observe the morphological properties of the polystyrene micro-spheres array. A relative good result can be easily obtained by a spinning speed of 2000 rpm for 30 second, when the solution concentration is around 10 wt.%. Furthermore, the polydimethylsiloxane soft mold was replicated from the-fabricated polystyrene micro-spheres array master and was then imprinted onto the photosensitive hybrid film under UV-irradiation and thus the micro-lens arrays built in the photosensitive hybrid sol-gel film were obtained.

Two-Dimensional Photonic Crystal Surfactant Detection

We developed a novel two-dimensional (2-D) crystalline colloidal array photonic crystal sensing material for the visual detection of amphiphilic molecules in water. A close-packed polystyrene 2-D array monolayer was embedded in a poly(N-isopropylacrylamide) (PNIPAAm)-based hydrogel film. These 2-D photonic crystals placed on a mirror show intense diffraction that enables them to be used for visual determination of analytes. Binding of surfactant molecules attaches ions to the sensor that swells the PNIPAAm-based hydrogel. The resulting increase in particle spacing red shifts the 2-D diffracted light. Incorporation of more hydrophobic monomers increases the sensitivity to surfactants.

Simultaneous Surface-Enhanced Raman Spectroscopy (SERS) and Atomic Force Microscopy (AFM) for Label-Free Physicochemical Analysis of Lipid Bilayers

Large-scale two-dimensional (2D) arrays of metallic nanostructures formed by thin-film evaporation over hexagonally close-packed polystyrene spheres are established substrates for surface-enhanced Raman spectroscopy (SERS). By using these substrates with an integrated atomic force microscopy (AFM) and inverted Raman spectroscopy system, simultaneous topographical imaging and high-sensitivity chemical mapping can be performed. In this paper, we have used this technique to investigate supported bilayers of long-chain fatty acids and phospholipids deposited by the Langmuir–Blodgett (LB) and spin-coating techniques. Nanosphere lithography (NSL) substrates created from 384 and 1002 nm polystyrene spheres and silver (Ag) deposition on glass and sapphire substrates were characterized for SERS in terms of their structure, distribution, and level of enhancement. SERS mappings of rhodamine 6G (R6G) and p-aminothiophenol (p-ATP) monolayers on the 384 nm substrates demonstrate high and uniform enhancement at a micrometer scale. The enhancement was sufficiently high to enable measurement of SERS spectra for arachidic acid (AA) and dipalmitoylphosphatidylcholine (DPPC) layers on sapphire/Ag substrates. The roughness of these substrates (<2 nm) was lower than for glass/Ag (∼5 nm); therefore, simultaneous to SERS it was possible to measure the topography of the samples by AFM and determine the number of layers of AA and DPPC. This study shows the potential of the combined AFM/SERS technique for spectral and topographical characterization of phospholipid bilayers. This may prove to be an interesting approach for further studies with more complex heterogeneous lipid mixtures aiming to measure spatially resolved features such as microdomains.