梯度结构胶体光子晶体的制备及光子禁带调节

以改进的对流自组装方法制备层数可控的胶体光子晶体, 并通过各向同性氧等离子体(O₂ Plasma)刻蚀构造出梯度结构, 进一步通过金(Au)及无定形硅(Si)的可控沉积调节梯度结构胶体光子晶体的光子禁带, 并将该梯度结构用于罗丹明B的荧光发射增强.     

Nanoparticle-mediated epitaxial assembly of colloidal crystals on patterned substrates

We have studied the assembly of 3-D colloidal crystals from binary mixtures of colloidal microspheres and highly charged nanoparticles on flat and epitaxially patterned substrates created by focused ion beam milling. The microspheres were settled onto these substrates from dilute binary mixtures. Laser scanning confocal microscopy was used to directly observe microsphere structural evolution during sedimentation, nanoparticle gelation, and subsequent drying. After microsphere settling, the nanoparticle solution surrounding the colloidal crystal was gelled in situ by introducing ammonia vapor, which increased the pH and enabled drying with minimal microsphere rearrangement. By infilling the dried colloidal crystals with an index-matched fluorescent dye solution, we generated full 3-D reconstructions of their structure including defects as a function of initial suspension composition and pitch of the patterned features. Through proper control over these important parameters, 3-D colloidal crystals were created with low defect densities suitable for use as templates for photonic crystals and photonic band gap materials.     

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.     

Dye/gelled colloidal photonic crystal composites and their reversible pH-responsive optical behaviors

We introduced dyes, the colors of which are variable by changing the pH of their medium solutions, into gelled colloidal photonic crystals (GCPCs) and investigated their reversible pH-responsive optical behaviors. When the extinction position of the dye overlaps with the Bragg peak of the GCPC, the Bragg-diffracted light can be trapped in the GCPC; when the extinction position of the dye is shifted out of the Bragg peak of the GCPC, the Bragg diffracted light is free and can escape out of the GCPC. The optical behaviors of dye/gelled colloidal photonic crystal composites are reversible to the pH changes of their surrounding medium.     

敏感性有序大孔水凝胶的模板合成与表征

多孔材料由于孔道相互连通、比表面积大等特性而在吸附、离子交换,特别是在催化等领域中具有广泛应用价值．当孔道均匀且有序排列时,如果其间距与可见光波长相匹配时,则可对光产生调制作用,得到光子带隙材料,在未来的信息处理等方面将发挥重要作用．目前,人们以单分散的微粒有序排列的胶体晶为模板制备了各种有序大孔材料,     

表面富含羧基的单分散交联聚合物微球的快速自组装制备胶体晶的研究

在20～70℃范围内,用垂直沉积的方法可使表面富含羧基的单分散交联聚合物微球在不同的基底上快速自组装成三维有序的胶体晶.不同粒径的微球形成的胶体晶其光禁带峰位不同,因此可调控不同波长的光在胶体晶中的传播.利用紫外-可见光谱研究了胶体晶的光禁带峰位与组成其微球粒径之间的关系.结果表明,随着构成胶体晶微球粒径的增大,胶体晶光禁带峰位发生了红移,而随着入射光角度的增大,胶体晶的光禁带峰位发生了蓝移.利用原子力显微镜和扫描电子显微镜研究了其它条件对聚合物微球有序排列的影响,发现聚合物微球在pH值为3.0～13.0范围内可以形成三维有序自组装胶体晶.这是由于在不同的pH值下,聚合物微球表面发生羧基化及去羧基化反应,导致在自组装过程中微球之间和微球与介质之间作用力的变化     

Microwave-assisted self-organization of colloidal particles in confining aqueous droplets

Monodisperse aqueous emulsion droplets encapsulating colloidal particles were produced in the oil phase, and controlled microwave irradiation of the aqueous drop phase created spherical colloidal crystals by so-called evaporation-induced self-organization of the colloidal particles. Unlike usual colloidal crystals, colloidal crystals in spherical symmetry (or photonic balls) possessed photonic band gaps for the normal incident light independent of the position all over the spherical surface. While the consolidation of colloidal particles in emulsion droplets in an oven took several hours, the present microwave-assisted evaporation could reduce the time for complete evaporation to a few tens of minutes. Under the microwave irradiation, the aqueous phase in emulsions was superheated selectively and the evaporation rate of water could be controlled easily by adjusting the microwave intensity. The result showed that the packing quality of colloidal crystals obtained by the microwave-assisted self-organization was good enough to show photonic band gap characteristics. The reflectance of our photonic balls responded precisely to any change in physical properties including the size of colloidal particles, refractive index mismatch, and angle of the incident beam. In particular, for polymeric particles, the photonic band gap could be tuned by the intensity of microwave irradiation, and the reflection color was red-shifted with stronger microwave irradiation. Finally, for better photonic band gap properties, inverted photonic balls were prepared by using the spherical colloidal crystals as sacrificial templates.     

Tailoring photonic crystals with nanometer-scale precision using polyelectrolyte multilayers

In this paper, we describe a rapid, accurate, and convenient method for postsynthetically tuning the optical properties of colloidal photonic crystals. High quality photonic crystal films are first synthesized and then coated iteratively with layers of water-soluble polyelectrolytes. The coating process results in nanometer-scale shifts in the photonic stop band, a process which has been monitored by theoretical modeling. The results suggest a fundamentally different, reproducible layering mechanism inside the confined spaces of the colloidal crystal where polyelectrolyte multilayers are less densely packed.     

Dry etching of colloidal crystal films

Two types of non-close-packed colloidal crystal films were prepared by etching the films made of polystyrene nanospheres using a hyperthermal neutral beam of oxygen gas. Etching without sintering above glass transition temperature of the polymer particles resulted in the non-close-packed structure of the nanospheres, in which polystyrene nanospheres in different lattice planes touched each other due to the reduction in the size of the nanospheres that occurred during the etching process. In contrast, a different non-close-packed structure with inter-connecting networks between etched nanospheres was generated by annealing of the colloidal crystal and a subsequent etching process. The photonic bandgap could be tuned during this dry etching of colloidal photonic crystals. This connected open structure could be used as a template for a silica inverse opal by chemical vapor deposition. An alternative dry etching process, reactive ion etching, mainly affected the morphology of particles near the top surface, and only a slight change in the stop band position of the colloidal crystal film was observed.     

Vapor detection enabled by self-assembled colloidal photonic crystals

Here we report the sensitive and reversible detection of vapors by using self-assembled colloidal photonic crystals. The condensation of various vapors in the interstitials of silica colloidal photonic crystals leads to red-shift and amplitude reduction of optical stop bands. A linear relationship between wavelength shift and vapor partial pressure has been observed for a variety of vapors including ethanol, water, and toluene. Importantly, the sensitivity of colloidal photonic crystal-based vapor detectors can be improved by nearly two orders of magnitude by using a new full-peak analysis technique that takes advantage of the manifest amplitude reduction of optical stop bands during vapor condensation. Optical simulation based on a scalar-wave approximation model shows that the predicted optical responses during vapor condensation in colloidal photonic crystals agree well with experimental results. The condensation of vapors between submicrometer-scale microspheres, a topic that has received little examination, has also been investigated by both experiments and theoretical calculations. Predictions based on a modified Kelvin equation match with the experiments for a wide range of vapor partial pressures.     

Controlled synthesis, growth mechanism, and properties of monodisperse CdS colloidal spheres

Highly monodisperse submicrometer CdS colloidal spheres (CSCS) with a controllable and tunable size (between 80 and 500 nm) have been synthesized through a facile solvothermal technique. Owing to the controllability of the reaction process, the growth mechanism of the colloidal spheres has been elucidated in detail. The whole growth process can be summarized as homogenous and slow nucleation of nanocrystals, formation of "cores" through 3D-oriented attachment of nanocrystals, and further surface-induced growth to monodisperse colloidal spheres through in situ formation and random attachment of additional nanocrystals. It has been demonstrated that the obtained CSCS colloidal particles are able to be assembled into films which show characteristic stop band gaps of photonic crystals. By using the CSCS as a template, Ag2S, Bi2S3, Cu2S, HgS, and Sb2S3 colloidal spheres, which are difficult to obtain directly, have also been prepared successfully through ion exchange.     

Directional Study of the Optical Properties of Tb3+‐ and Eu3+‐Doped Nanoparticles Embedded in Silica Photonic Crystals

The effects of the stop band (SB) in colloidal photonic crystals composed of silica spheres containing Eu³⁺‐ and Tb³⁺‐doped yttria nanoparticles are analysed. Reflection and transmission spectra indicate movement of the stop band, due to the 111 series of planes, towards shorter wavelengths with increasing angle of observation. The profile of the emission spectra is modified by the presence of the SB depending on the angle of measurement. Such a modification is more effective for a narrow emission band and it is thus more evident in the case of Tb³⁺ than Eu³⁺. An angular effect is also observed in the lifetime, which presents two maxima and one minimum. In the case of Tb³⁺ the maxima are at observation angles of 35 and 50°, and the minimum at 45°. We attribute this behaviour to penetration of the excitation beam at 475 nm modulated by the stop band. The ions excited in this way emit from different depths in the crystal, and therefore their lifetime will be affected differently by the same stop band, depending on the thickness of the crystal that must be crossed. Eu³⁺ shows a similar but less pronounced effect for two reasons: first, the main stop band (due to the 111 planes) is not effective at the excitation wavelength of 392 nm; second, the broadness of the Eu³⁺ emission is comparable to the width of the SB, and a decrease in the transition rate at the wavelength of the SB maximum is compensated by an increase at the sides of the SB.     

Gelation of colloidal crystals without degradation in their transmission quality and chemical tuning

A single-domain colloidal crystal with high transmission quality, prepared by a shear-induced process, was fixed as a hydrogel film by photopolymerization. Upon gelation, the original optical quality was almost perfectly preserved. By replacing the solvent, the gelled crystal could be converted to smaller lattice constant crystals without significant degradation in its transmission characteristics. The conversion results in a stop-band wavelength coverage across the entire visible light range.     

Doped colloidal photonic crystal structure with refractive index chirping to the [111] crystallographic axis

A three-dimensionally ordered array of close-packed colloidal spheres, a photonic crystal structure in which the refractive index of the medium interstitial lattice in a colloidal crystal spatially changes in the [111] crystallographic axis, is demonstrated. The colloidal photonic crystal structure with refractive index chirping was produced by infiltration of a monomer and organic dopants with a high refractive index into a silica opal, followed by interfacial gel polymerization. The resulting photonic crystal structure has a gradually varying stop band at each different (111) plane in the face-centered cubic (fcc) crystal structure at a normal incidence. This novel structure exhibited optical characteristics that have band-gap broadening by the superposition of stop bands at each plane of the crystal with different dielectric functions. Moreover, the refractive index perturbation in the [111] fcc opal also showed a defect state within a pseudo-photonic band gap. This new type of photonic crystal structure should be useful for the band-gap engineering of photonic-band-gap materials.     

Control of the optical band structure of liquid crystal infiltrated inverse opal by a photoinduced nematic-isotropic phase transition

Recently, photonic band gap (PBG) crystals with lattice parameters comparable to the wavelength of light have attracted much attention, because they offer unique ways in which to control the propagation of light. PBG crystals have applications in laser, quantum optical devices, and so on. For many of these applications, it is important to have the capability of tuning the photonic band structures. The fabrication of such tunable PBG crystals is still a challenge. In this paper, we proposed that switchable PBG crystals could be realized by taking advantage of the phase transition in liquid crystals induced by the photoisomerization of azo dyes. A dynamic change in the optical stop band was demonstrated. Such photoswitchable PBG crystals provide a method by which light can be routed using light.     

Polystyrene@TiO2 core-shell microsphere colloidal crystals and nonspherical macro-porous materials

High-quality and stable PS@TiO(2) core-shell microsphere colloidal crystals were prepared by electrostatic colloid stabilization combined with two-substrate vertical deposition method. The polyelectrolyte stabilized colloids self-assembled into face-centered cubic arrays with the (111) face perpendicular to the substrate. These colloidal crystals are gifted with high mechanical stability toward the flow of solution. Structure-property correlations were made using scanning electron microscopy and UV-vis-NIR spectroscopy. Optical spectra showed the presence of an L-stopband peak in the photonic band structure. Besides, these PS@TiO(2) colloidal crystals can be used as templates to fabricate the nonspherical macro-porous materials, and complete band gaps can be more easily obtained from such structure than from their spherical counterparts due to their lower symmetries. This work will hold the promise of enhanced photonic band gap materials.     

Enhancement of electronic excitation energy transfer in the colloidal crystals of colloidal silica suspensions doped with fluorescent dyes

The efficiency of electronic excitation energy transfer from photo-excited rhodamine 110 (Rh110, energy donor) to rhodamine B (RhB, energy acceptor) in an exhaustively deionized colloidal silica suspension has been studied. This colloidal suspension shows Bragg reflection due to the formation of colloidal crystals and the Bragg-peak wavelength is controllable by the volume fraction of the silica spheres. When the Bragg-peak wavelength matches with the fluorescence band of Rh110, a depletion was observed in the Rh110 fluorescence spectrum. This means the fluorescence of Rh110 is partially trapped due to the Bragg reflection inside the crystal lattice. In the coexistence of RhB, the enhancement of RhB fluorescence intensity was observed. These facts clearly indicate the trapped photon energy of Rh110 is efficiently transferred to RhB within the colloidal crystals. The quantitative measurements showed that the enhancement of the transfer efficiency is 20% (or slightly more) in the present experimental conditions.     

A class of supported membranes: formation of fluid phospholipid bilayers on photonic band gap colloidal crystals

We report the formation of a new class of supported membranes consisting of a fluid phospholipid bilayer coupled directly to a broadly tunable colloidal crystal with a well-defined photonic band gap. For nanoscale colloidal crystals exhibiting a band gap at the optical frequencies, substrate-induced vesicle fusion gives rise to a surface bilayer riding onto the crystal surface. The bilayer is two-dimensionally continuous, spanning multiple beads with lateral mobilities which reflect the coupling between the bilayer topography and the curvature of the supporting colloidal surface. In contrast, the spreading of vesicles on micrometer scale colloidal crystals results in the formation of bilayers wrapping individual colloidal beads. We show that simple UV photolithography of colloidal crystals produces binary patterns of crystal wettabilities, photonic stopbands, and corresponding patterns of lipid mono- and bilayer morphologies. We envisage that these approaches will be exploitable for the development of optical transduction assays and microarrays for many membrane-mediated processes, including transport and receptor-ligand interactions.     

High-speed fabrication of patterned colloidal photonic structures in centrifugal microfluidic chips

In this paper, we report a rapid and facile method for fabricating colloidal photonic crystals inside microchannels of radially symmetric microfluidic chips which were made using soft-lithography. As the suspension of monodisperse silica or polystyrene latex spheres was driven to flow through the channels under the action of centrifugal force, the colloidal spheres were quickly assembled into face centered cubic arrangement which had a few photonic stop bands. The soft-microfluidic channels and cells confined the colloidal crystals into designed patterns. The optical reflectance was modulated by the refractive-index mismatch between the colloidal particles and the solvent in the interstices between the particles. Therefore, the present microfluidic chips with built-in colloidal photonic crystals can be used as in-situ optofluidic microsensors for high throughput screening or light filters in integrated adaptive optical devices.     

Tunable optical stop band of silica shell photonic crystals

In this study, optical stop band of three-dimensional silica shell photonic crystals is tuned by adjusting inner diameter and shell thickness of hollow silica spheres. The silica shell photonic crystals are fabricated by sintering crystalline arrays, which are assembled from polystyrene/silica core–shell spheres by an improved vertical deposition method. The inner diameter and the shell thickness are controlled by diameter of polystyrene spheres and concentration of tetraethoxysilane. The results of transmission spectra show that there is an evident red shift of optical stop band as the inner diameter and the shell thickness increase. The red shift of optical stop band is due to variations in the inter-planar spacing and the effective refractive index of silica shell photonic crystals, which result from the variations of the inner diameter and the shell thickness of hollow silica spheres.