Nonspherical colloidal crystals fabricated by the thermal pressing of colloidal crystal chips

Nonspherical colloids and their ordered arrays may be more attractive in applications such as photonic crystals than their spherical counterparts because of their lower symmetries, although such structures are difficult to achieve. In this letter, we describe the fabrication and characterization of colloidal crystals constructed from nonspherical polyhedrons. We fabricated such nonspherical colloidal crystals by pressing spherical polymer colloidal crystal chips at a temperature slightly lower than the glass-transition temperature (T(g)) of these polymer colloids. During this process, the polymer microspheres were distinctively transformed into polyhedrons according to their crystal structures, whereas the long-range order of the 3D lattice was essentially preserved. Because a working temperature lower than T(g) effectively prevented the colloidal crystals from fusing into films, the spherical colloidal crystals were transformed greatly under pressure, which lead to obvious change in the optical properties of colloidal crystals. Besides their special symmetry and optical properties, these nonspherical colloidal crystals can be used as templates for 2D or 3D structures of special symmetry, such as 2D nano-networks. We anticipate that this fabrication technique for nonspherical colloidal crystals can also be extended to nonspherical porous materials.     

Focused ion beam micromachining and computation of polymeric photonic band gap

This article introduces a new approach to the achievement of low cost devices for optical telecommunications. For this purpose, the implementation of polymer components and of the WDM method show several advantages. A polymeric photonic band gap lattice can effectively assume demultiplexing at the wavelength of 1.55 μm without energy dissipation. First, the computation of the geometrical parameters designing a polymer photonic crystal by means of the finite‐difference‐time‐domain method, implemented with Bloch functions, is presented here. Second, the achievement of 2D polymer lattices by a dry process, the focused ion beam milling, is exposed. The experimental conditions for the achievement of a master are discussed on the basis of the milling performances and of the polymers physical properties. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2993–3002, 2007     

Enhancement of the fluorescence intensity of DNA intercalators using nano-imprinted 2-dimensional photonic crystal

We have fabricated polymer-based 2-dimensional photonic crystals that play a key role in enhancing the fluorescence of DNA intercalators. Highly ordered 2-dimensional photonic crystals possessing triangle-shaped and nm-sized hole arrays were fabricated on a 100 μm thick polymer film using nano-imprint lithography. Samples of double-stranded DNAs (sizes: 4361 and 48502 bp; concentration: 1 pM to 10 nM) were adsorbed on the surface of the 2-dimensional photonic crystal by electrostatic interactions and then treated with intercalators. It is found that the fluorescence intensity of the intercalator is enhanced by a factor of up to 10 compared to the enhancement in the absence of the 2-dimensional photonic crystal. Fluorescence intensity increases with increasing length and concentration of the DNAs. If the 2-dimensional photonic crystal is used as a Bragg reflection mirror, the enhancement of fluorescence intensity can be easily observed using a conventional spectrofluorometer. These results suggest that the printed photonic crystal offers a great potential for highly sensitive intercalator-based fluorescent detection of DNAs.

Modification of Adhesive and Latex Properties for Starch Nanoparticle‐Based Pressure Sensitive Adhesives

Starch nanoparticle (SNP)‐based pressure sensitive adhesives (PSAs) with core‐shell particle morphology (starch nanoparticle core/acrylic polymer shell) are produced via seeded, semi‐batch emulsion polymerization at 15 wt% SNP loading (relative to total polymer weight) and 40 wt% latex solids. Crosslinker and chain transfer agent (CTA) are introduced to the acrylic shell polymer formulation at a range of concentrations according to a 3² factorial design to tailor the latex and adhesive properties of SNP‐based latexes. The crosslinker and CTA show no significant effect on polymerization kinetics, particle size, and viscosity. Latex gel content is predicted using an empirical model, which is a function of crosslinker and CTA concentration. Both the gel content and glass transition temperature strongly affect the adhesive properties (tack, peel strength, and shear strength) of the SNP‐based latex films. 3D response surfaces for the adhesive properties are constructed to facilitate the design of SNP‐based PSAs with desired properties.     

Fabrication of Photonic Crystal Structures by Femtosecond Laser-Induced Photopolymerization of Organic-Inorganic Film

We report on a fabrication of photonic crystal structures in organic-inorganic hybrid films by a laser interference technique. Films containing the methacrylic group, which is photopolymerable by an adequate laser light, are prepared using a sol-gel technique from a mixture of organosilicate alkoxide and zirconium alkoxide modified by methacrylic acid. For the photopolymerization, the coated films on glass substrate are exposed to the interference light which is arranged with a square lattice in about 1 m spacing. From microscopic images of microstructures produced by the photopolymerization, the influence of changes in conditions such as pre-bake temperature, photoinitiator and irradiation energy (laser power and duration time) on periodic structure is investigated. Adjusting the conditions, 2D and 3D photonic crystal structures with the micrometer-order period are formed in organo-silicate-zirconate hybrid materials.     

光子晶体研究进展

光子晶体是最近10余年间提出的新概念和新材料。本文简述了光子晶体的主要特性,重点阐述了光子晶体的制作方法,特别是高分子材料制作分子晶体的几种新方法。     

电化学制备P型硅基二维光子晶体优化参数

利用光刻技术与碱性腐蚀等工艺预写晶格图样,采用电化学腐蚀方法在P〈100〉型硅基底制备二维大孔硅光子禁带结构.结果表明:在预写有晶格图样的P〈100〉型硅基底上由电化学阳极氧化制备的二维大孔硅,其孔洞的生长速率、深宽比及表/侧面形貌与电解质配比方案及阳极电流密度均密切相关.在优化的电化学工艺参数下得到的空气洞阵列,具有近乎完美的二维四方晶格,晶格常数为3.8μm,孔洞直径约3.0μm,孔洞深宽约90μm,深宽比达30.该方法可用于制备在中红外或近红外波段具有完全二维光子带隙的光子晶体.     

Enhanced electron field emission properties of high aspect ratio silicon nanowire-zinc oxide core-shell arrays

The enhanced electron field emission (EFE) properties of high aspect ratio, vertically aligned SiNW-ZnO core-shell arrays are presented. These core-shell arrays are prepared by a thin, controlled, highly crystalline and conformal coating of zinc oxide as shell using the plasma assisted-atomic layer deposition (PA-ALD) route on vertically aligned silicon nanowire arrays core. The core-shell nanostuctures are confirmed by HRTEM imaging along with the individual elemental mapping demonstrating the conformal deposition of 10 nm ZnO on the SiNWs. EFE properties of va-SiNW-ZnO core-shell arrays showed a high emission current density of 51 μA cm(-2) and a low turn on field of 7.6 V μm(-1) (defined at a current density of 1 μA cm(-2)) compared to the 3.2 μA cm(-2) emission current density and 9.1 V μm(-1) turn on field for SiNWs. The field enhancement factor (β) of 4227 for the devices demonstrates that these core-shell nanowire arrays are excellent field-emitters. Such an enhancement in the field emission originates from the details of the band structure of this peculiar material combination resulting in good electron transport from SiNW to ZnO as evident from the band diagram of the core-shell material. This is further supported by the conducting AFM studies where lowering in threshold voltage by 1 eV confirms the role of ZnO coating in the enhancement of the emission characteristics.     

Hybrid material based on ST–AA photonic crystal core and ZnO particle shell

The aim of this study was to obtain a hybrid material based on a polymer photonic crystal core and inorganic ZnO shell with potential applications in optoelectronic devices or photocatalysts. For this reason, ZnO particles were obtained both in the absence and presence of ST–AA particles using a chemical reduction method for metal salts. The inhibited growth mechanism of inorganic particles generated in the presence of polymer latex was noticed. The products were characterized by SEM, EDX, TEM, DLS, and UV–vis.     

Introduction of a planar defect in a molecularly imprinted photonic crystal sensor for the detection of bisphenol A

This paper reports the preparation of a molecularly imprinted inverse opal hydrogel containing a 2D defect layer, by combining the Langmuir-Blodgett technique and the photonic crystal template method. By coupling the exceptional characteristics of molecularly imprinted polymers, sensitive to the presence of a target molecule, and those of photonic crystals in a single device, we could obtain a defect-embedded imprinted photonic polymer consisting in a three-dimensional, highly-ordered and interconnected macroporous array, where nanocavities complementary to analytes in shape and binding sites are distributed. As a proof of concept, we prepared a three-dimensional macroporous array of poly(methacrylic acid) (PMAA) containing molecular imprints of bisphenol A (BPA) and a planar defect layer consisting in macropores of different size. The optical properties of the resulting inverse opal were investigated using reflection spectroscopy. The defect layer was shown to enhance the sensitivity of the photonic crystal material, opening new possibilities towards the development smart optical sensing devices.     

A Luminescent Dicyanodistyrylbenzene-based Liquid Crystal Polymer Network for Photochemically Patterned Photonic Composite Film

A novel photonic composite film based on a luminescent dicyanodistyrylbenzene-based liquid crystal polymer network (LCN)was fabricated by using a silica colloidal crystal as a template.The upper part of inverse opal structure and the luminescence characteristics of dicyanodistyrylbenzene-based moiety endowed the resulting bilayer photonic film with structural color arising from coherent Bragg reflection and fluorescence properties,respectively.A fluorescence enhancement phenomenon was observed in the photonic film due to the overlap between the reflection band and emission band of the fluorescent LCN.More importantly,the photo-induced irreversible Z/E photoisomerization of dicyanodistyrylbenzene-based moiety in the photonic film led to both a reflection spectral shift and an observable fluorescence variation.On the basis of this effective phototuning process,microscopic patterning ofphotonic film was developed under both fluorescence mode and reflection mode.The work demonstrated here provides a new route to construct photo-responsive photonic film.     

Stiff,Multistimuli‐Responsive Supramolecular Hydrogels as Unique Molds for 2D/3D Microarchitectures of Live Cells

Supramolecular hydrogels constructed through molecular self‐assembly of small molecules have unique stimuli‐responsive properties; however, they are mechanically weak in general, relative to conventional polymer gels. Very recently, we developed a zwitterionic amino acid tethered amphiphilic molecule 1 , which gave rise to a remarkably stiff hydrogel comparable with polymer‐based agarose gel, retaining reversible thermal‐responsive properties. In this study, we describe that rational accumulation of multiple and orthogonal noncovalent interactions in the supramolecular nanofibers of 1 played crucial roles not only in the mechanical reinforcement but also in the multistimuli responsiveness. That is, the zwitterionic amino acid moiety and the C C double bond unit of the hydrogelator 1 can function as a pH‐responsive unit and a light‐responsive unit, respectively. We also demonstrated that this stiff and multistimuli‐responsive supramolecular hydrogel 1 is applied as a unique mold for 2D and 3D‐patterning of various substances. More significantly, we succeeded in the fabrication of a collagen gel for spatial patterning, culturing, and differentiation of live cells by using hydrogel 1 molds equipped with 2D/3D microspace channels (100–200 μm in diameter).     

Wired-enzyme core-shell Au nanoparticle biosensor

We report a fully integrated core-shell nanoparticle system responsive to glucose. The system is comprised of self-assembled glucose oxidase and an osmium molecular wire on core-shell Au nanoparticles. Characterization of the functional nanoparticles by spectroscopy, quartz crystal microbalance and electrochemical techniques has shown that the catalytically active shell has a structure as designed and all components are active in the self-assembled multilayer shell. Furthermore, amperometric reagentless detection of glucose and contactless photonic biosensing by the Os(II) resonant Raman signal have been demonstrated. The enzymatic reduction of FAD by glucose and further reduction of the Raman silent Os(III) by FADH 2 yields a characteristic enzyme-substrate calibration curve in the millimolar range. Furthermore, coupling of electronic resonant Raman of the osmium complex with the SERS amplification by Au NPs plasmon resonance has been demonstrated which leads to an extra enhancement of the biosensor signal. We present a proof of concept extending the work done with planar surfaces to core-shell NPs as an advance in the design of glucose-responsive chemistry detected by SERS-like methods.     

有序金属纳米壳材料

有序金属纳米壳结构特别是有序中空纳米壳及大孔结构兼具了光子晶体和金属纳米壳结构的光学特性,引起了国内外学者的广泛关注。本文详细介绍了有序金属纳米壳材料的制备方法与步骤,主要包括胶体晶模板的组装、所需金属壳层的制备以及胶体晶模板的去除三步,并对各步的制备方法及特点进行了描述。此外,本文还对金属纳米壳有序材料的各种应用进行了综述,简要分析了目前存在的问题并展望了今后该材料的研究方向。     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

Colloidal crystalline array of hydrogel-coated silica nanoparticles: effect of temperature and core size on photonic properties

This paper reports the fabrication of a photonic crystal made of hydrogel-coated colloidal nanoparticles, which can act as an optical sensor in visible and near-infrared region triggered by temperature. The synthetic scheme involves silanization of silica nanoparticles followed by radical-initiated precipitation polymerization forming a thermoresponsive polymer coating. These core–shell nanostructures self-assemble to produce colloidal crystalline array (CCA). The main advantages of self-assembly approach are experimental simplicity, possibility of 3D assembly and inexpensive mass production. Photon correlation spectroscopy results revealed a very interesting new phenomenon of showing a distinct break near the lower critical solution temperature along with a set of two-step curves, in the plot of mean hydrodynamic radius vs. temperature, which can be attributed to the breakage of two different types of hydrogen-bonding. The lattice parameters of these CCAs and hence their sensor properties can be effectively tuned by varying the core-size and temperature, which in turn changes the composite particle size as well as shape and hence volume fraction. In Reflectance measurements, the position of the stop-band was found to be directly proportional to the core-size, whereas the appearance of a second diffraction peak was correlated to the non-spherical nature of the nanocomposites supported by atomic force microscope images and possibly due to the existence of a second phase. The occurrence of such high-order multiple Bragg’s diffraction peak certainly opens a new door towards nanophotonic sensor devices.     

Infrared dielectric mirrors based on thin film multilayers of polystyrene and polyvinylpyrrolidone

Thin film polymer multilayers were prepared by spin coating alternating layers of polystyrene and polyvinylpyrrolidone. Samples with 10, 20, 30, 40, and 50 layers were prepared with individual layer thickness values in the range 223–508 nm. These samples were measured using a Fourier transform infrared spectrometer and were found to display narrow photonic band gaps (～ 0.04 to 0.06 μm wide) in their spectral response over the wavelength range 1.6 ? 2.6 μm. The position of the photonic band gaps was controlled by varying the thickness of the individual layers within the multilayer structures. This was achieved by varying the spin speed used during the deposition of the polymer layers. The peak reflectance of the multilayers was controlled by varying the number of layers within the multilayer samples giving values in the range 20–80% (corresponding to transmittances of 80–20%). Calculated transmittance spectra were also obtained using an optical transfer matrix method. These calculated spectra were shown to be in good agreement with the experimental data obtained. These experiments demonstrate a facile approach to the production of low cost dielectric mirrors that have tailored photonic properties over a range of wavelengths that are currently important for applications in fibre optic based telecommunications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Templated‐Assembly of CsPbBr3 Perovskite Nanocrystals into 2D Photonic Supercrystals with Amplified Spontaneous Emission

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr₃ perovskite NC colloids into large area (1 cm²) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr₃ 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.     

Mimicking natural fibrous structures of opals by means of a microemulsion-mediated hydrothermal method

Silica-based nanomaterials are of great interest because of their potential applications in constructing electronic and optoelectronic nanodevices. Especially significant are those that combine the properties of photonic crystal with a fibrous semiconductor structure. Here we report the use of microemulsion droplet systems as a simple and controllable route for the synthesis of 3D opals materials with an unusual fibrous microstructure similar to those that exist in nature. By this method, we demonstrate the creation of very long fibrils of 30-50 nm diameter and more than 20 μm length showing simultaneous short and long wavelength light emissions and band gap values (5.50 and 4.41 eV) comparable to those obtained for silicon-based metal oxide semiconductors.