Silicon Inverse Opal—A Platform for Photonic Bandgap Research

This article focuses attention on recent research on the silicon inverse opal, the first self‐assembled or bottom–up synthetic photonic crystal to exhibit a complete photonic bandgap (PBG) at 1.5 μm^[1] in accordance with theoretical predictions.^[2] The silicon inverse opal has since proven to be a useful platform for assembling on‐chip films^[3] and in‐chip patterns,^[4] engineering extrinsic defects,^[5] mapping photon density of states,^[6] switching light with light, and inhibiting spontaneous emission.^[7] Also, new and exciting colloidal‐crystal‐based structures are being developed based on experimental and theoretical knowledge acquired for the synthesis of inverted silicon photonic crystals.^[8–10] It has also inspired the idea of the silicon inverse opal heterostructure, a theoretical construct that could enable an all‐optical microchip for single mode diffractionless waveguiding of light in air throughout a bandwidth of more than 70 nm at 1.5 μm.^[11]     

Inkjet Printing of Patterned,Multispectral, and Biocompatible Photonic Crystals

Patterning of photonic crystals to generate rationally designed color‐responsive materials has drawn considerable interest because of promising applications in optical storage, encryption, display, and sensing. Here, an inkjet‐printing based strategy is presented for noncontact, rapid, and direct approaches to generate arbitrarily patterned photonic crystals. The strategy is based on the use of water‐soluble biopolymer‐based opal structures that can be reformed with high resolution through precise deposition of fluids on the photonic crystal lattice. The resulting digitally designed photonic lattice formats simultaneously exploit structural color and material transience opening avenues for information encoding and combining functions of optics, biomaterials, and environmental interfaces in a single device.     

Chemical Approaches to Three‐Dimensional Semiconductor Photonic Crystals

We review recent efforts to make three‐dimensional semiconductor photonic crystals using self‐assembly techniques. These approaches, which utilize a synthetic opal as a template to shape the semiconductor material (see Figure), provide a simple and inexpensive alternative to lithographic methods. Since the resulting structures can, in principle, have a complete photonic bandgap – a property that would allow ultimate control over the flow of light – these materials may have serious implications for modern photonics.     

pH响应性光子晶体

响应性光子晶体(Responsive photonic crystals,RPCs)具有无毒、无标记、低消耗和裸眼可视的优点,pH响应性光子晶体(pH-RPCs)为食品安全、生物医药、水体环境等领域提供了一种简便的检测方式。目前主要发展了胶体粒子组装体/反蛋白石、层状堆叠和全息三种结构类型的pH-RPCs。本文在介绍光子晶体(Photonic crystals,PCs)pH响应原理的基础上,从制备方法、结构特点和pH响应性能(如灵敏度、响应时间、可视化)等方面对上述pH-RPCs进行了详细的综述,分析总结了它们各自的优势和不足,并对其未来的发展进行了展望。     

Simulation and fabrication of binary colloidal photonic crystals and their inverse structures

Theoretical and experimental investigations have demonstrated that full bandgaps are not easy to achieve in the face-centered cubic (fcc) unary and binary structures; even for unary inverse opals with high refractive index network, the bandgaps are not as large as 1D or 2D structures. In this work, we simulated the bandgap of a binary inverse opal, which is over 16% larger than that of a unary inverse crystal. Two kinds of binary colloidal crystals and their inverse structures have been fabricated by a horizontal deposition method.     

Thermal Responsive Photonic Crystal Achieved through the Control of Light Path Guided by Phase Transition

Responsive photonic crystal is widely considered in the field of anti‐counterfeiting and information encryption because of their structural color changes caused by external stimulation. However, the response signal is usually achieved by adjusting the periodic lattice constant based on Bragg's law with volume changes. Thus, it is a great challenge to achieve the response of photonic crystals by non‐array parameter control. Herein, novel thermal responsive photonic crystal (TRPC) with low angle dependent structural color is fabricated by introducing poly(ethylene glycol) into the structure of low angle dependent SnO₂ inverse opal. The response is achieved through the control of light path guided by phase transition and the significant volume change caused by the change of traditional array parameters can be effectively avoided. Meanwhile, the low angle dependent structural color of TRPC can effectively reduce the interference of observation angle change to response signal caused by external thermal stimulation. Patterned responsive photonic crystals with temperature gradient response are easily obtained by combining confinement self‐assembly and direct template method, and the patterns can be presented and hidden by the control of light path, showing great potential in anti‐counterfeiting and information encryption fields.     

Inside Front Cover: Line Defects Embedded in Three‐Dimensional Photonic Crystals (Adv. Mater. 15/2005)

The inside cover illustrates an approach to creating line defects embedded in the interior of a self‐assembled photonic crystal, as reported by Zhao and co‐workers on p. 1917. Photoresist patterns are first constructed on the surface of a silica opal film by conventional optical photolithography. After regrowth of the silica colloidal crystal, photoresist line defects are successfully introduced into the self‐assembled silica colloidal crystal. Further processing results in an inverse opal with air‐core line defects embedded in its interior, which provides a prototype for future optical waveguide devices based on self‐assembled three‐dimensional photonic crystals.     

Photonic bandgap calculations with Dirichlet-to-Neumann maps

A simple and efficient method for computing bandgap structures of two-dimensional photonic crystals is presented. Using the Dirichlet-to-Neumann (DtN) map of the unit cell, the bandgaps are calculated as an eigenvalue problem for each given frequency, where the eigenvalue is related to the Bloch wave vector. A linear matrix eigenvalue problem is obtained even when the medium is dispersive. For photonic crystals composed of a square lattice of parallel cylinders, the DtN map is obtained by a cylindrical wave expansion. This leads to eigenvalue problems for relatively small matrices. Unlike other methods based on cylindrical wave expansions, sophisticated lattice sums techniques are not needed.     

反蛋白石结构光子晶体及其应用的研究

反蛋白石结构光子晶体因具有完全光子带隙、制备材料广泛、特殊的周期结构、大的比表面积和连通的孔洞结构,近年来在自发辐射的调制、提高光催化反应速率和染料敏化太阳能电池反应速率等领域成为研究热点之一,并且在光、电、催化、传感、显示、检测等领域有着巨大的应用价值。介绍了反蛋白石结构光子晶体的基本概念及制备方法,阐述了反蛋白石结构在材料自发辐射的调制、能量传递的调制、促进物理化学反应、外界环境响应材料等方面的作用及其应用。     

光子晶体传感器的研究进展

光子晶体是一类具有光子能带和带隙的新型光学材料,近年来已成为传感器技术领域的研究热点。光子晶体微腔、光子晶体波导、光子晶体光纤在传感器领域得到了广泛应用,而凝胶光子晶体、反蛋白石光子晶体、分子印迹光子晶体则实现了化学生物传感器的"裸眼检测技术"。重点分类介绍了一维、二维、三维光子晶体的制备及其在传感器领域的应用进展。     

Biomaterial‐Based “Structured Opals” with Programmable Combination of Diffractive Optical Elements and Photonic Bandgap Effects

Naturally occurring iridescent systems produce brilliant color displays through multiscale, hierarchical assembly of structures that combine reflective, diffractive, diffusive, or absorbing domains. The fabrication of biopolymer‐based, hierarchical 3D photonic crystals through the use of a topographical templating strategy that allows combined optical effects derived from the interplay of predesigned 2D and 3D geometries is reported here. This biomaterials‐based approach generates 2D diffractive optics composed of 3D nanophotonic lattices that allow simultaneous control over the reflection (through the 3D photonic bandgap) and the transmission (through 2D diffractive structuring) of light with the additional utility of being constituted by a biocompatible, implantable, edible commodity textile material. The use of biopolymers allows additional degrees of freedom in photonic bandgap design through directed protein conformation modulation. Demonstrator structures are presented to illustrate the lattice multifunctionality, including tunable diffractive properties, increased angle of view of photonic crystals, color‐mixing, and sensing applications.     

Photonic Crystal Hydrogel Enhanced Plasmonic Staining for Multiplexed Protein Analysis

Plasmonic nanoparticles are commonly used as optical transducers in sensing applications. The optical signals resulting from the interaction of analytes and plamsonic nanoparticles are influenced by surrounding physical structures where the nanoparticles are located. This paper proposes inverse opal photonic crystal hydrogel as 3D structure to improve Raman signals from plasmonic staining. By hybridization of the plasmonic nanoparticles and photonic crystal, surface‐enhanced Raman spectroscopy (SERS) analysis of multiplexed protein is realized. It benefits the Raman analysis by providing high‐density “hot spots” in 3D and extra enhancement of local electromagnetic field at the band edge of PhC with periodic refractive index distribution. The strong interaction of light and the hybrid 3D nanostructure offers new insights into plasmonic nanoparticle applications and biosensor design.     

Photonic Glasses: A Step Beyond White Paint

Self‐assembly techniques are widely used to grow ordered structures such as, for example, opal‐based photonic crystals. Here, we report on photonic glasses, new disordered materials obtained via a modified self‐assembling technique. These random materials are solid thin films which exhibit rich novel light diffusion properties originating from the optical properties of their building blocks. This novel material inaugurated a wide range of nanophotonic materials with fascinating applications, such as resonant random lasers or Anderson localization.     

Silicon‐Based Photonic Crystals

Photonic crystals can be thought of as optical analogues of semiconductors. Here recent advances in photonic crystals based on silicon are reviewed. After summarizing the theory of photonic bandgap materials, the preparation and linear optical properties of 1D, 2D, and 3D silicon‐based photonic crystals are discussed. Laterally structured porous silicon with a defect line is shown in the Figure.     

Plasmonic Enhancement in BiVO4 Photonic Crystals for Efficient Water Splitting

Photo‐electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar‐to‐H₂ conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano‐architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible‐light‐active photoanode constructed from BiVO₄ photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm^?2 at 1.23 V versus RHE, which is among the highest for oxide‐based photoanodes and over 4 times higher than the unstructured planar photoanode.     

Combining Bottom‐Up Self‐Assembly with Top‐Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order

Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom‐up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack‐free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top‐down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano‐ and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.     

NaGd(WO4)2:Yb3+/Tm3+反蛋白石光子晶体的制备与上转换发光调制研究

三维光子晶体具有长程有序的结构特点, 在可见和近红外光谱范围内有着广泛的应用。光子晶体的一个重要性质是其对嵌入其中的发光中心自发辐射具有调制作用。本研究利用自组装和模板辅助法制备高质量的三维NaGd(WO₄)₂:Yb³⁺/Tm³⁺反蛋白石光子晶体, 探究了光子带隙对Tm³⁺离子上转换荧光发射与发光动力学的调制作用。通过对比分析发现, 由于反蛋白石光子晶体独特的周期性大孔结构和光子带隙效应, 处于光子带隙内的Tm³⁺离子¹G₄-³H₆的发光强度被抑制约45%, 自发辐射速率(SDR)被抑制约30%, 同时上转换局域热效应得到有效的调制。本实验结果对探索新型高效稀土掺杂上转换发光材料和提高上转换发光效率有指导意义。     

Photonic Crystals

Abstract

In this paper, we review the early motivation for photonic crystal research which was derived from the need for a photonic bandgap in quantum optics. This led to a series of experimental and theoretical searches for the elusive photonic bandgap structures: those three-dimensionally periodic dielectric structures which are to photon waves, as semiconductor crystals are to electron waves. We shall describe how the photonic semiconductor can be ‘doped’, producing tiny electromagnetic cavities. Finally, we shall summarize some of the anticipated implications of photonic band structure for quantum electronics and the prospects for the creation of photonic crystals in the optical domain.     

Inverse Opal Scaffolds with Gradations in Mineral Content for Spatial Control of Osteogenesis

The design and fabrication of inverse opal scaffolds with gradations in mineral content to achieve spatial control of osteogenesis are described. The gradient in mineral content is established via the diffusion‐limited transport of hydroxyapatite nanoparticles in a closely packed lattice of gelatin microbeads. The mineral‐graded scaffold has an array of uniform pores and interconnected windows to facilitate efficient transport of nutrients and metabolic wastes, ensuring high cell viability. The graded distribution of mineral content can provide biochemical and mechanical cues for spatially regulating the osteogenic differentiation of adipose‐derived stromal cells. This new class of scaffolds holds promise for engineering the interfaces between mineralized and unmineralized tissues.     

Inverse Opal Scaffolds with an Embossed Surface Pattern Prepared from Sticky Golf‐Ball‐Shaped Microparticle Assemblies

Inverse opal scaffolds presenting an embossed‐pattern surface are prepared from colloidal crystal assemblies of uniformly sized golf‐ball‐shaped microparticles. Post‐treatments, such as thermal annealing during the bridging of the microparticles for opal preparation, are avoided to prevent deterioration of surface patterns of the sacrificial template. This presents a new approach to increase the surface‐area‐to‐volume ratio (SAV) by the alteration of morphological features in sophisticated 3D structures that remain largely unexamined owing to difficulties in their preparation. Previous results observed in 2D surfaces that show effective performance improvement through an increase in contact area, especially in biomedical applications, also appear applicable to patterned inverse opal scaffolds based on comparable results obtained from cell cultures. As the field of application of opal and inverse opal structures is expanding due to their unique structural advantages, such as 3D interconnectivity and periodic structures, our strategy opens the door for the use of patterned surfaces on highly sophisticated 3D structures, improving their performance via an increase in SAV.