快速响应聚合物光子晶体研究进展

响应性光子晶体以其亮丽的结构色彩及光学信号对外场刺激的响应性变化,在化学传感、智能显示等领域具有重要的应用前景.本文综述了快速响应聚合物光子晶体的研究进展.首先从原理上阐述了影响溶胀型光子晶体响应速率的因素,系统总结了针对不同因素提高其响应速率的研究工作,着重探讨了溶胀型光子晶体水凝胶的尺寸、聚合物链段的物理化学性能(包括多孔结构和亲疏水性)、凝胶网络的交联度等因素对响应速率的影响.同时也简要介绍了影响非溶胀型响应性光子晶体,如光、电、磁、机械力等外场诱导体系折光指数变化的响应性光子晶体的响应速率的因素.最后展望了响应性光子晶体的热点研究方向.这些工作对于提高光子晶体的响应速率,发展其在实时分析、在线检测等领域的应用具有重要意义.     

化学响应性光子晶体

光子晶体是一种具有光子带隙结构的周期性电介质材料,如果将响应性材料组装到光子晶体结构中,所形成的光子晶体的带隙结构则对外界环境的变化具有响应性,而被称为响应性光子晶体。响应性光子晶体作为光子晶体的一个新领域,由于其在传感器,生物医学,临床检测等方面的潜在应用,近几年受到广泛关注。根据外界环境的不同,响应性光子晶体可简单分为化学响应性光子晶体、物理响应性光子晶体和生物响应性光子晶体等。本文将对化学响应性光子晶体的国内外研究动态做一简要介绍,重点介绍以下五种化学响应性光子晶体:金属离子响应光子晶体、pH响应光子晶体、氧化还原响应光子晶体、葡萄糖响应光子晶体和光化学响应光子晶体。     

Recent advances in spherical photonic crystals: Generation and applications in optics

Spherical photonic crystals (PCs), generated by assembly of monodisperse colloidal nanospheres in a spherical confined geometry, attract great attention recently owing to their potential applications in the fields of displays, sensors, optoelectronic devices, and others. Compared to their conventional film or bulk counterparts, the optical stop band of the spherical PCs is independent of the rotation under illumination of the surface of a fixed incident angle of the light, broadening their applications. In this paper, we will review recent advances in the field of spherical PCs including design, preparation and potential applications. Various preparation strategies for spherical PCs, including solvent-evaporation induced crystallization method, microfluidic-assisted approach, and others are outlined. Their applications based on the unique optical properties (such as photonic band gaps and structural colors) for sensing and displaying are then presented, followed by the perspective of this emerging field.     

P(St-AM)核壳聚合物微球的制备及其光子晶体膜

采用一步乳液聚合法,调节引发剂用量,制备了不同粒径的具有核壳结构的功能性聚(苯乙烯-丙烯酰胺)乳胶微球.用透射电子显微镜表征了乳胶微球的核壳结构和粒径,所制微球的粒径分别为195,217,234和255 nm.用红外光谱对微球的化学成分进行了表征,证实聚丙烯酰胺已包覆在聚苯乙烯外层.通过竖直沉积自组装法制备了聚合物微球的光子晶体薄膜.扫描电子显微镜表征了所制光子晶体膜的表面形貌,反射和透射光谱表征了光子禁带.结果表明,聚合物微球以面心立方紧密堆积,其(111)面与基底平行;微球粒径不同,光子晶体的光子禁带不同.制备了不同光子禁带的光子晶体,禁带分别位于473,515,574和630 nm,相应的薄膜分别呈蓝色、绿色、黄色和红色,对于光子晶体的拓展和应用具有重要的意义.     

光子晶体的制备及应用

光子晶体（PC）是具有光子带隙的周期性电介质结构，频率落在光子带隙中的光将被禁止传播。本文对光子晶体的能带结构、带隙的产生、制备方法及应用作了简要的介绍，重点介绍了光子晶体的制备技术及其在光电领域中的应用前景。     

Patterned Colloidal Photonic Crystals

Colloidal photonic crystals (PCs) have been well developed because they are easy to prepare, cost‐effective, and versatile with regards to modification and functionalization. Patterned colloidal PCs contribute a novel approach to constructing high‐performance PC devices with unique structures and specific functions. In this review, an overview of the strategies for fabricating patterned colloidal PCs, including patterned substrate‐induced assembly, inkjet printing, and selective immobilization and modification, is presented. The advantages of patterned PC devices are also discussed in detail, for example, improved detection sensitivity and response speed of the sensors, control over the flow direction and wicking rate of microfluidic channels, recognition of cross‐reactive molecules through an array‐patterned microchip, fabrication of display devices with tunable patterns, well‐arranged RGB units, and wide viewing‐angles, and the ability to construct anti‐counterfeiting devices with different security strategies. Finally, the perspective of future developments and challenges is presented.     

蛋白石及反蛋白石結構光子晶體

光子晶体是由不同介电常数的材料构成的一种空间周期性结构，它能够在特定方向上禁阻、控制和操纵光子的运动。目前，已制备的光子晶体具有几种不同的结构类型，本文主要综述了蛋白石、反蛋白石结构光子晶体的制备方法及其光子带隙的影响因素。     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

三维SiO2欧泊模板溶剂热法制备硫化锌光子晶体

以单分散二氧化硅微球在重力场下自组装得到的三维有序欧泊(opal)为模板，采用溶剂热法在模板空隙内生长ZnS晶体，从而制备高质量的硫化锌基光子晶体. 通过X射线衍射(XRD)和Raman光谱证明ZnS晶体为闪锌矿结构且晶体质量较好，并对其生长机理进行了讨论. 通过场发射扫描电子显微镜(FESEM)和紫外-可见分光光度计对所合成的ZnS/opal复合物与ZnS反欧泊结构进行了表征，结果表明两种结构都保持了欧泊三维有序性，并且在Г-L方向(垂直于(111)方向)上出现了布拉格衍射峰，说明其具有良好的光子晶体特性.     

Fabrication of 3D polymeric photonic arrays and related applications

This review article describes the state-of-art methodologies, mainly self-assembly routes, which are in practice to fabricate photonic crystals (PCs) for advanced applications. The self-assembly of colloidal building blocks is an effective, affordable, and tunable approach to fabricate varieties of photonic materials of desired shapes and surface areas. Because of easy fabrication and controlled performance factors, PCs emerged as a potential platform for designing and developing optical devices with desired features such as photonic bandgap, high reflectance/transmittance, low loss, and lasing in the visible range of wavelengths. To develop next-generation optoelectronics and optical system, significant efforts are being made to explore novel and cost-effective fabrication methods to design and develop 3D-PCs platform, which is covered in this mini-review. The challenges, potential alternatives, and prospects of self-assembled 3D PCs are also discussed in this review.     

磺化聚苯乙烯胶体晶的红外光谱分析

单分散乳胶体系可以通过自组装形成有序的胶体晶结构 ,在窄波段光过滤器[1] 、生物医学传感器[2 ] 、智能化学传感器[3] 等领域具有重要的应用价值 .最近 ,人们以此有序结构作为模板 ,制备了有序孔材料[4～ 7] .另外 ,此有序结构在仿生学如模拟蛋白石等有序结构等方面也具有重要意义[8] .但是 ,一般的单分散体系如聚苯乙烯体系所形成的有序结构都属于硬性材料 ,缺乏对外场的响应特性 .此外 ,微球表面没有功能性基团 ,很难与其它物质兼容 ,这使得其作为模板合成其它复合材料的潜力大大降低 .本实验室通过对聚合物胶体晶进行改性 ,使其成为功…     

胶体光子晶体的平面介电常数缺陷

为引入特殊的光学性质,通常需要在三维光子晶体中人为可控地引入缺陷.通过改变局部结构单元的尺寸或介电常数,相应地引入给体或受体掺杂,带来不同的缺陷态.以前文献报道的向胶体光子晶体中引入缺陷,常会因为同时引入尺寸和介电常数掺杂,给掺杂性质的界定带来困难.本文中,我们结合对流自组装法和L-B膜法,在实心二氧化硅微球组成的三维光子晶体内引入尺寸相同的二氧化硅空心球(与实心球相比具有不同折光率)组成的单层平面缺陷,或者在空心球晶体内引入实心球缺陷层,构成实心-空心-实心或空心-实心-空心的三明治结构,在不破坏整体晶格的同时,在三维胶体光子晶体中引入单一的平面介电常数缺陷.     

光子晶体的制备与应用进展

光子晶体概念的提出到现在已有20多年,由于其特有的带隙和缺陷结构可实现对光子传播的控制,与传统的基于半导体晶体的电子技术相比更具优势,是未来光子计算机和光子通讯技术研发的核心。近年来,基于新材料、新方法制备的具有复杂结构的光子晶体不断涌现,其应用范围也从较早的波导、光开关、反射镜拓展到传感器、超棱镜、微透镜、太阳能电池、增强LED发光、光存储、生物芯片、仿生等新兴领域。本文结合了最新的研究状况,探讨了光子晶体的制备与应用进展。     

Non‐Brownian Particle‐Based Materials with Microscale and Nanoscale Hierarchy

Colloidal crystals are interesting materials owing to their customizable photonic properties, high surface area, and analogy to chemical structures. The flexibility of these materials has been greatly enhanced through mixing particles with varying sizes, compositions, and surface charges. In this way, distinctive patterns or analogies to chemical stoichiometries are produced; however, to date, this body of research is limited to particles with nanoscale dimensions. A simple method is now presented for bottom‐up assembly of non‐Brownian particle mixtures to create a new class of hierarchically‐ordered materials that mimic those found in nature (both in pore distribution as well as stoichiometry). Additionally, these crystals serve as a template to create particle‐based inverted crystalline structures with customizable properties.     

Colloidal assembly: the road from particles to colloidal molecules and crystals

Colloidal particles may be considered as building blocks for materials, just like atoms are the bricks of molecules, macromolecules, and crystals. Periodic arrays of colloids (colloidal crystals) have attracted much interest over the last two decades, largely because of their unique photonic properties. The archetype opal structures are based on close-packed arrays of spheres of submicrometer diameter. Interest in structuring materials at this length scale, but with more complex features and ideally by self-assembly processes, has led to much progress in controlling features of both building blocks and assemblies. The necessary ingredients include colloids, colloidal clusters, and colloidal "molecules" which have special shapes and the ability to bind directionally, the control over short-range and long-range interactions, and the capability to place and orientate these bricks. This Review highlights recent experimental and theoretical progress in the assembly of colloids larger than 50 nm.     

垂直排列法组装胶体晶体的最新进展

光子晶体是一种具有光子带隙的新型功能材料.利用胶体粒子自组装三维光子晶体由于其制备过程比较经济、简单,从而为很多人所关注.目前报道的方法已有多种.其中垂直排列法的简便易行使得其受到了广泛的研究,但另一方面这种方法本身的缺点也限制了它的使用范围.针对这种情况,很多研究机构提出了他们的改进方法.本文简要概述了在这一方面的最新进展,并且在本实验室已能够制备任意单分散、均一尺寸二氧化硅粒子的基础上,采用恒温快速蒸发自组装法得到了高质量的胶体晶体排列.     

Photoswitching properties of photonic band gap material containing azo-polymer liquid crystal

A photochemically tunable photonic crystal was prepared by infiltration of the polymer liquid crystal (LC) having azo-chromophores in a SiO₂ inverse opal structure. The SiO₂ inverse opal film infiltrated with the polymer LC reflected a light corresponding to the periodicity as well as the refractive indices of the inverse opal structure. Linearly polarized light irradiation caused the shift of the reflection band to longer wavelength more than 15 nm. This is caused by the formation of uniaxially anisotropic molecular orientation of the polymer LC. The switched state was stable under interior light, and reversible switching of the reflection band can be achieved by the linearly and circularly polarized light irradiation. This photoswitching property will be suitable not only for various optical materials, but also for introduction of defects in the photonic crystals.     

胶体晶体研究进展

重点阐述了有关胶体晶体的制备方法、以胶体晶体为模板制备的大孔材料，以及利用胶体晶体的三维有序结构、结构颜色等特性制备光子晶体、传感器等研究的进展。     

Opal and inverse opal photonic crystals: Fabrication and characterization

Three-dimensional photonic crystals made of close-packed polymethylmethacrylate (PMMA) spheres or air spheres in silica, titania and ceria matrices have been fabricated and characterized using SEM, XRD, Raman spectroscopy and UV–Vis transmittance measurements. The PMMA colloidal crystals (opals) were grown by self-assembly from aqueous suspensions of monodisperse PMMA spheres with diameters between 280 and 415 nm. SEM confirmed the PMMA spheres crystallized uniformly in a face-centred cubic (fcc) array, and UV–Vis measurements show that the colloidal crystals possess pseudo photonic band gaps in the visible and near-IR regions. Inverse opals were prepared by depositing silica (SiO₂), titania (TiO₂) or ceria (CeO₂) in the voids of the PMMA colloidal crystals using sol-gel procedures, then calcining the resulting structure at 550 °C to remove the polymer template. The resulting macroporous materials showed fcc ordering of air spheres separated by thin frameworks of amorphous silica, nanocrystalline titania or nanocrystalline ceria particles, respectively. Optical measurements confirmed the photonic nature of the inverse opal arrays. UV–Vis data collected for the opals and inverse opals obeyed a modified Bragg’s law expression that considers both diffraction and refraction of light by the photonic crystal architectures. The versatility of the colloidal crystal template approach for the fabrication of macroporous oxide structures is demonstrated.     

Anomalous light scattering in photonic cholesteric liquid crystals

ABSTRACT

We have carried out polarisation and angle-resolved measurements of the light scattered from photonic cholesteric liquid crystals. Both in samples doped with laser dyes and in inactive (non-doped) samples we have observed pronounced directional dependences of the scattered light, finding angular ranges where the scattering is greatly enhanced and regions where the effect is almost suppressed. Moreover, the total amount of scattered light has also been found to depend strongly on the polarisation and direction of the incident beam. All the results have been interpreted successfully in terms of a simple expression proposed for the scattering cross section, in which the density of states of the ingoing and outgoing beams plays a major role. The expression would be applicable not only to cholesteric liquid crystals but to any one-dimensional photonic material.