Photochemically Controlled Photonic Crystals

We have developed photochemically controlled photonic crystals that may be useful in novel recordable and erasable memories and/or display devices. These materials can operate in the UV, visible, or near‐IR spectral regions. Information is recorded and erased by exciting the photonic crystal with ～ 360 nm UV light or ～ 480 nm visible light. The information recorded is read out by measuring the photonic crystal diffraction wavelength. The active element of the device is an azobenzene‐functionalized hydrogel, which contains an embedded crystalline colloidal array. UV excitation forms cis‐azobenzene while visible excitation forms trans‐azobenzene. The more favorable free energy of mixing of cis‐azobenzene causes the hydrogel to swell and to red‐shift the photonic crystal diffraction. We also observe fast nanosecond, microsecond, and millisecond transient dynamics associated with fast heating lattice constant changes, refractive index changes, and thermal relaxations.     

Poly(vinyl alcohol) Rehydratable Photonic Crystal Sensor Materials

We developed a new photonic crystal hydrogel material based on the biocompatible polymer poly (vinyl alcohol) (PVA), which can be reversibly dehydrated and rehydrated, without the use of additional fillers, while retaining the diffraction and swelling properties of polymerized crystalline colloidal arrays (PCCA). This chemically modified PVA hydrogel photonic crystal efficiently diffracts light from the embedded crystalline colloidal array. This diffraction optically reports on volume changes occurring in the hydrogel by shifts in the wavelength of the diffracted light. We fabricated a pH sensor, which demonstrates a 350 nm wavelength shift between pH values of 3.3 and 8.5. We have also fabricated a Pb(+2) sensor, in which pendant crown ether groups bind lead ions. Immobilization of the ions within the hydrogel increases the osmotic pressure due to the formation of a Donnan potential, swelling the hydrogel and shifting the observed diffraction in proportion to the concentration of bound ions. The sensing responses of rehydrated PVA pH and Pb(+2) sensors were similar to that before drying. This reversibility of rehydration enables storage of these hydrogel photonic crystal sensors in the dry state, which makes them much more useful for commercial applications.     

Poly(vinyl alcohol) Rehydratable Photonic Crystal Sensor Materials

We developed a new photonic crystal hydrogel material based on the biocompatible polymer poly (vinyl alcohol) (PVA), which can be reversibly dehydrated and rehydrated, without the use of additional fillers, while retaining the diffraction and swelling properties of polymerized crystalline colloidal arrays (PCCA). This chemically modified PVA hydrogel photonic crystal efficiently diffracts light from the embedded crystalline colloidal array. This diffraction optically reports on volume changes occurring in the hydrogel by shifts in the wavelength of the diffracted light. We fabricated a pH sensor, which demonstrates a 350 nm wavelength shift between pH values of 3.3 and 8.5. We have also fabricated a Pb⁺² sensor, in which pendant crown ether groups bind lead ions. Immobilization of the ions within the hydrogel increases the osmotic pressure due to the formation of a Donnan potential, swelling the hydrogel and shifting the observed diffraction in proportion to the concentration of bound ions. The sensing responses of rehydrated PVA pH and Pb⁺² sensors were similar to that before drying. This reversibility of rehydration enables storage of these hydrogel photonic crystal sensors in the dry state, which makes them much more useful for commercial applications.     

Photoinduced Tuning of Optical Stop Bands in Azopolymer Based Inverse Opal Photonic Crystals

Photo‐tunable photonic crystals were prepared from three dimensional (3D) colloidal crystal templates using a photoresponsive azopolymer. For the preparation of azopolymer infiltrated photonic crystals, silica colloidal crystals were fabricated by gravity sedimentation, a self‐assembly technique. The interstitial voids between colloidal particles were filled with azopolymer and azopolymer inverse opals were produced by treatment with aqueous hydrofluoric acid. These photonic crystals exhibited stop bands in their transmission spectra measured in the normal incidence to the (111) plane of face centered cubic (fcc). The photonic bandgap of the azopolymer infiltrated opal and inverse opal could be controlled by the refractive index change due to the photoinduced orientation of azobenzene chromophores. When the azopolymer photonic crystals were irradiated with linearly polarized light, their bandgap positions were shifted to shorter wavelength regions with increasing irradiation time. This behavior experimentally produced a photoinduced orientation of the azobenzene groups in parallel with the incidence of the excitation light. Through such an out‐of‐plane orientation of azo chromophores, parallel to the [111] fcc crystallographic axis, the effective refractive index of the photonic crystal medium was decreased. Therefore, a blue‐shift in bandgap positions was consequently induced with 20–40 nm tuning ranges. The out‐of‐plane orientation was confirmed by angular resolved absorption spectral measurements.     

Multifaceted and Nanobored Particle Arrays Sculpted Using Colloidal Lithography

A novel method of fabricating multifaceted and nanobored particle arrays via colloidal lithography using colloidal‐crystal layers as masks for anisotropic reactive‐ion etching (RIE) is reported. The shape of the sculpted particles is dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, the RIE conditions, and the matrix (or mask) structure in colloidal lithography. Arrays of non‐spherical particles with sculpted shapes, which to date could not otherwise be produced, are fabricated using a tilted anisotropic RIE process and the layer‐by‐layer growth of a colloidal mask. These non‐spherical particles and their ordered arrays can be used for antireflection surfaces, biosensors, and nanopatterning masks, as well as non‐spherical building blocks for novel colloidal crystals. In addition, polymeric particles with patterned holes of controlled depths obtained by the present method can be applied to the fabrication of functional composite particles.     

Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals

High quality opal‐like photonic crystals containing graphene are fabricated using evaporation‐driven self‐assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle‐dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time‐temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution‐processable nanomaterial based photonics.     

Fabrication of Photonic Microbricks via Crack Engineering of Colloidal Crystals

Evaporation‐induced self‐assembly of colloidal particles is one of the most versatile fabrication routes to obtain large‐area colloidal crystals; however, the formation of uncontrolled “drying cracks” due to gradual solvent evaporation represents a significant challenge of this process. While several methods are reported to minimize crack formation during evaporation‐induced colloidal assembly, here an approach is reported to take advantage of the crack formation as a patterning tool to fabricate microscopic photonic structures with controlled sizes and geometries. This is achieved through a mechanistic understanding of the fracture behavior of three different types of opal structures, namely, direct opals (colloidal crystals with no matrix material), compound opals (colloidal crystals with matrix material), and inverse opals (matrix material templated by a sacrificial colloidal crystal). This work explains why, while direct and inverse opals tend to fracture along the expected {111} planes, the compound opals exhibit a different cracking behavior along the nonclose‐packed {110} planes, which is facilitated by the formation of cleavage‐like fracture surfaces. The discovered principles are utilized to fabricate photonic microbricks by programming the crack initiation at specific locations and by guiding propagation along predefined orientations during the self‐assembly process, resulting in photonic microbricks with controlled sizes and geometries.     

High-quality SiO2 Colloidal Crystal Fabricated by Controllable Vertical Deposition Method

Monodispersed silica microspheres with diameter of 353 nm were assembled into photonic crystal in ethanol colloidal suspensions of varied silica volume fraction at different temperature and humidity by means of controllable vertical deposition method. The surface morphology and optical properties were studied by SEM and UV-Vis-NIR. It was found that the high quality silica colloidal photonic crystals were obtained from ethanol solutions with environment temperature between 45℃ and 55℃, humidity between 66% and 76%, the volume fraction of microspheres is between 0.8% and 1.5%, The ordered close-packed photonic crystal fabricated by controllable vertical deposition method had the two photonic bandgaps in the visible light band and near infrared band,     

倾斜底涂法制备聚苯乙烯胶体晶体及其光学特性研究

采用倾斜底涂法将单分散的聚苯乙烯胶体微球自组装生长成为胶体晶体,并用扫描电子显微镜和紫外-可见光分光光度计对其形貌和光学特性进行测量。结果表明,聚苯乙烯微球自组装为面心立方密堆积结构,胶体晶体的光子带隙位于可见光波段。分别对不同胶体颗粒的粒径、悬浮液的浓度、基片倾斜角度及环境温度等制备条件下生成的聚苯乙烯光子晶体样品逐一分类对比,分析了影响光子带隙宽度和深度的因素。     

Light‐Driven Electrohydrodynamic Instabilities in Liquid Crystals

The induction of electrohydrodynamic instabilities in nematic liquid crystals through light illumination are reported. For this purpose, a photochromic spiropyran is added to the liquid crystal mixture. When an electrical field is applied in the absence of UV light, the homeotropic liquid crystal reorients perpendicular to the electrical field driven by its negative dielectric anisotropy. Upon exposure to UV light, the nonionic spiropyran isomerizes to the zwitterionic merocyanine form inducing electrohydrodynamic instabilities which turns the cell from transparent into highly scattering. The reverse isomerization to closed‐ring spiropyran form occurs thermally or under visible light, which stops the electrohydrodynamic instabilities and the cell becomes transparent again. It is demonstrated that the photoionic electrohydrodynamic instabilities can be used for light regulation. Local exposure, either to drive the electrohydrodynamics or to remove them enables the formation of colored images.     

Reversible Quadruple Switching with Optical,Chiroptical, Helicity,and Macropattern in Self‐Assembled Spiropyran Gels

Enantiomeric glutamate gelators containing a spiropyran moiety are designed and found to self‐assemble into a nanohelix through gelation. Upon alternating UV and visible light irradiation, the spiropyran experiences a reversible change between a blue zwitterionic merocyanine state and a colorless closed ring state spiropyran in supramolecular gels. This photochromic switch causes a series of subsequent changes in the optical, chiroptical, morphological properties from supramolecular to macroscopic levels. While the solution of the gelator molecules does not show any circular dichroism (CD) signal in the region of 250–700 nm due to the fact that the chromophore is far from the chiral center, the gel shows chiroptical signals such as CD and circularly polarized luminescence (CPL) because of the chirality transfer by the self‐assembly. These signals are reversible upon alternating UV/vis irradiation. Therefore, a quadruple optical and chiroptical switch is developed successfully. During such process, the self‐assembled nanostructures from the enantiomeric supramolecular gels also undergo a reversible change between helices and fibers under the alternating UV and visible light trigger. Furthermore, a rewritable material fabricated from their xerogels on a glass is developed. Such rewritable material can be efficiently printed over 30 cycles without significant loss in contrast and resolution using UV and visible light.     

Stimuli‐Directing Self‐Organized 3D Liquid‐Crystalline Nanostructures: From Materials Design to Photonic Applications

3D photonic nanostructures with desirable functionalities in the visible light region and beyond have been recently given vast and increasing attentions because of the ability to control or confine electromagnetic waves in all three dimensions. Although substantial progress has been made in fabricating 3D nanostructures by means of lithography and nanotechnology, various bottlenecks still need to be overcome, and developing soft 3D stimuli‐directed nanostructures with tailored properties remains a challenging but exciting work. In this context, soft nanotechnology—i.e., exploiting self‐organized soft materials in nanotechnology—is emerging as a vibrant and burgeoning field of research in the bottom‐up nanofabrication of intelligent stimuli‐driven 3D photonic materials and devices. Liquid‐crystalline materials undoubtedly represent such a marvelous dynamic system that combines the liquid‐like fluidity and crystal‐like ordering from molecular to macroscopic material levels. Importantly, being “soft” makes the materials responsive to various stimuli such as temperature, light, mechanical force, and electric and magnetic fields as well as chemical and electrochemical reactions, resulting in a fascinating tunability of dynamic photonic bandgaps in the 3D nanostructure that provides numerous opportunities in all‐optical integrated circuits and next‐generation communication systems. Here, the development of 3D photonic nanostructures is reviewed, culminating with perspectives for the future scope and challenges of these emerging soft 3D photonic nanostructures towards device applications.     

Dendron‐Stabilized Liquid Crystalline Blue Phases with an Enlarged Controllable Range of the Photonic Band for Tunable Photonic Devices

Liquid crystalline blue phases (BPs) show excellent potential for application in tunable photonic devices because they possess the unique optical property that the selective 3D Bragg diffraction in a visible wavelength region can be continuously shifted using an electric field. A new approach to simultaneously extend the wavelength range of field‐induced Bragg diffraction shift and the temperature range of thermodynamically stable BPs is critically needed. Here, a new BP material system is shown using a dendron molecule to extend simultaneously the two BP ranges. One is the temperature range of thermodynamically stable BPs, which is expanded from 2.1 to 4.6 °C. The other is the reversible maximum shift range of Bragg wavelength on the electric field, which is extended from 85 to 109 nm. The physical mechanism of the dendron‐stabilizing effect in BPs is discussed in terms of elastic property and orientational order of liquid crystal molecules.     

混合型Fe3O4@SiO2胶体光子晶体光传输特性的仿真分析

除了通过改变胶体粒子半径及晶格常数来实现对光子带隙的调控方式之外,能否利用不同尺寸粒子的混合精确控制胶体光子晶体的显色行为是人们关注的一个重要科学问题。在分析Fe₃O₄@SiO₂胶体光子晶体的带隙范围与介电常数、电磁波入射角度、晶格常数、颗粒尺寸、SiO₂包覆层厚度的依赖关系的基础上,利用数值仿真手段对不同尺寸粒子混合得到的光子晶体的光传输特性进行了研究。结果发现,两种粒径的磁性胶体粒子按不同质量比混合后,其光子带隙位置始终落在两种粒径胶体粒子各自形成光子晶体的带隙位置之间,且随着大粒径颗粒掺杂比的增加,反射光谱逐渐红移。这一结果证明混色原理对胶体光子晶体仍然是适用的。该结果对研究胶体光子晶体结构色的新型调控方式具有重要的参考价值。     

Light‐Driven and Light‐Guided Microswimmers

Light‐driven swimming particles hold great potential in wide applications ranging from next‐generation drug delivery to versatile microrobotic devices. It is desired that the self‐propelled microparticles should swim not only autonomously but also directionally to achieve their goals in their potential applications. This paper presents the first example of fully organic colloidal particles of a spiropyran‐terminated hyperbranched polymer that can be driven and meanwhile steered by a UV light source, swimming straight towards the UV source. The mean‐square velocities of the photochromic suspension particles are about 20 μm s^?1, and increase to about 54 μm s^?1 with the addition of NaCl of 0.5%. The phototactic propulsion is supposed to be originated from the UV irradiation‐induced interfacial tension gradient on the surface of the colloidal particles. This finding allows for the design of new microengines for next‐generation drug delivery systems, microrobotic devices, and self‐adaptive photocatalysts, etc.     

ZnO光子晶体的制备及其光子带隙特性研究

利用重力场下的自组装,将单分散的ZnO胶体颗粒悬浮液自组装为三维光子晶体.通过扫描电镜图谱、透射光谱对制得的ZnO光子晶体进行了表征.结果表明,这种方法可得到排列有序的光子晶体,并且改变反应条件可以控制ZnO胶体球的尺寸.制得的样品有较宽的光子禁带,且禁带波长位置随胶体球粒径的减小和前处理温度的降低而蓝移.当入射光角度逐渐增大时,禁带中心位置有规律地向短波长方向移动.     

Photopatterning Freestanding Chiral Nematic Mesoporous Organosilica Films

Chiral nematic mesoporous organosilica (CNMO) films are functionalized with a mixture of hydrophobic silanes and spiropyran compounds to create freestanding photochromic films that can be used for reversible photo­patterning. The mesoporosity and interconnected pore structure of the films imparted by the cellulose nanocrystal template enables a large cross‐section of the material to be functionalized. Thus, the materials show intense absorption spectra from the tethered spiropyran and rapid color changes when the porous films are irradiated with UV or white light. The spiropyran‐bound CNMO films behave as reversible sensors where metal binding to the spiropyran results in visible color changes detectable by the naked eye. These metals can be removed in the presence of ethanol and white light, regenerating the metal‐free film. The proof‐of‐concept demonstrated in this paper may help to develop new photochromic displays, security features, and patterns.     

垂直沉积法在GaAs衬底上制备有序SiO2胶体晶体

报道了一种利用直径为286nm的单分散SiO2胶体颗粒制备胶体晶体的方法。乙醇悬浮中的SiO2颗粒通过毛细作用力在垂直插入其中的GaAs衬底表面自组装成胶体晶体。扫描电子显微镜（SEM）和紫外-可见分光光度计对胶体晶体的形貌和光学特性进行了表征。结果显示,所得到的胶体晶体膜具有较好的三维有序结构。分析了退火对样品光子带隙的影响。     

Broadband Omnidirectional Diversion of Light in Hybrid Plasmonic‐Photonic Heterocrystals

Broadband, omnidirectional, and polarization‐independent diversion has been achieved of more than 90% of the light flow intensity off its incidence direction using hybrid metal–dielectric plasmonic‐photonic heterocrystals. These architectures were prepared by depositing metal film on the interface between two photonic crystals of different parameters. The magnitude of light losses was extracted from angle‐resolved measurements of transmission and reflectance spectra. Comparing these data for different stages of constructing the complex architecture, the diffraction in colloidal crystals, the excitation and radiative decay of short‐living surface plasmon polaritons in a corrugated metal film and the eigenmode mismatch at the interface between two different photonic crystals were identified as corroborating physical mechanisms behind the light diversion.     

Layer‐by‐Layer Growth of Multicomponent Colloidal Crystals Over Large Areas

Self‐assembly of different sized colloidal particles into multicomponent crystals results in novel material properties compared to the properties of the individual components alone. The formation of binary and, for the first time, ternary colloidal crystals through a simple and inexpensive confined‐area evaporation‐induced layer‐by‐layer (LBL) assembly method is reported. The proposed method produces high quality multicomponent colloidal crystal films over a broad range of particle size‐ratios and large surface areas (cm²) from silica/polystyrene colloidal suspensions of low concentration. By adjusting the size‐ratio and concentration of the colloidal particles, complex crystals of tunable stoichiometries are fabricated and their structural characteristics are further confirmed with reported crystal analogues. In addition, complex structures form as a result of the interplay of the template layer effect, the surface forces exerted by the meniscus of the drying liquid, the space filling principle, and entropic forces. Thus, this LBL approach is a versatile way to grow colloidal crystals with binary, ternary, or more complex structures.