The Optical Janus Effect: Asymmetric Structural Color Reflection Materials

Structurally colored materials are often used for their resistance to photobleaching and their complex viewing‐direction‐dependent optical properties. Frequently, absorption has been added to these types of materials in order to improve the color saturation by mitigating the effects of nonspecific scattering that is present in most samples due to imperfect manufacturing procedures. The combination of absorbing elements and structural coloration often yields emergent optical properties. Here, a new hybrid architecture is introduced that leads to an interesting, highly directional optical effect. By localizing absorption in a thin layer within a transparent, structurally colored multilayer material, an optical Janus effect is created, wherein the observed reflected color is different on one side of the sample than on the other. A systematic characterization of the optical properties of these structures as a function of their geometry and composition is performed. The experimental studies are coupled with a theoretical analysis that enables a precise, rational design of various optical Janus structures with highly controlled color, pattern, and fabrication approaches. These asymmetrically colored materials will open applications in art, architecture, semitransparent solar cells, and security features in anticounterfeiting materials.     

Tunable Structural Color Patterns Based on the Visible-Light-Responsive Dynamic Diselenide Metathesis

Structural color materials with reversible stimuli-responsiveness to external environment have been widely used in sensors, encryption, display, and other fields. Compared with other stimuli, visible light is highly controllable both temporally and spatially with less damage to materials, which is more suitable for structural color patterning. Herein, a new diselenide-containing shape memory material is prepared and used for creating patterns via visible light stimulus. In this system, the structural color originates from birefringence of stretched materials, whose shapes can be fixed while maintaining the mechanical stress. The fixed stress can be released by diselenide metathesis under visible light irradiation. By regulating the wavelength or irradiation time with a commercial projector, the pattern with tunable structural colors is realized and the structural color pattern can be erased and rewritten arbitrarily. During the patterning process, the optical signal is first stored as mechanical signal and then transformed back to optical signal. It is a new method for preparing visible-light-responsive structural color material and has great potential in display devices, anticounterfeiting labels, and data storage.     

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.     

Conversion of Carbon Dots from Fluorescence to Ultralong Room‐Temperature Phosphorescence by Heating for Security Applications

Stimuli‐responsive optical materials have received tremendous interest in the last several decades due to their numerous promising applications. Here, fluorescence emissive polymer carbon dots (F‐CDs), prepared with a simple heating treatment from ethylenediamine and phosphoric acid, are found to produce unexpected ultralong room‐temperature phosphorescence (URTP), which lasts for about 10 s with a lifetime of 1.39 s. This is the first example to achieve the conversion of a fluorescence material to URTP by means of an external heating stimulus. Further investigations reveal that the doping of N and P elements and self‐immobilization of the excited triplet species are likely mainly responsible for the observed URTP after the heating treatment, due to the facilitation of the intersystem crossing and formation of more compact cores for effective intraparticle hydrogen bonds, respectively. Importantly, this study also demonstrates the potential for aqueous dispersion of the F‐CDs as an advanced security ink for information encryption and anticounterfeiting; this is a feature that has not been reported before. This study is believed to open possibilities to extend stimuli‐responsive optical materials to rarely exploited phosphorescence‐relevant systems and applications, and also to provide a novel strategy to easily prepare URTP materials.     

非晶无序光子晶体结构色机理及其应用

结构色是一种由光学尺度的微纳结构与光相互作用形成干涉、衍射或散射而产生颜色的物理生色效应。与化学生色不同,结构色由于没有色素或者染料的参与,因此没有颜色褪色的现象,同时能够避免使用染料和色素带来的环境污染。目前结构色材料受到研究者和应用开发人员的广泛关注,大量的研究发现结构色可以来源于光子晶体与非晶光子晶体两种结构。光子晶体由规整的周期性结构组成,产生的颜色鲜艳却具有明显的角度依赖性。而非晶光子晶体,其"自身缺陷"导致的短程有序结构具备了各向同性的光子带隙、非虹彩效应、光局域化等特点,赋予了材料柔和亮丽不随角度变化的显色效果,可控的激光效应以及优良的发光效率,从而更能满足材料领域对光散射和光传输等方面的特殊需求。对非晶光子晶体的概念和结构,与可见光作用产生颜色的原理,以及制备非晶光子晶体的不同方法(平板刻蚀法、胶体颗粒自组装法、模板法、相分离法)做了详细的讨论,并对非晶光子晶体产生的结构色效应在光电器件、功能涂料和纺织材料等多个领域中的应用进行了展望。     

Lithographically Encrypted Inverse Opals for Anti‐Counterfeiting Applications

Colloidal photonic crystals possess inimitable optical properties of iridescent structural colors and unique spectral shape, which render them useful for security materials. This work reports a novel method to encrypt graphical and spectral codes in polymeric inverse opals to provide advanced security. To accomplish this, this study prepares lithographically featured micropatterns on the top surface of hydrophobic inverse opals, which serve as shadow masks against the surface modification of air cavities to achieve hydrophilicity. The resultant inverse opals allow rapid infiltration of aqueous solution into the hydrophilic cavities while retaining air in the hydrophobic cavities. Therefore, the structural color of inverse opals is regioselectively red‐shifted, disclosing the encrypted graphical codes. The decoded inverse opals also deliver unique reflectance spectral codes originated from two distinct regions. The combinatorial code composed of graphical and optical codes is revealed only when the aqueous solution agreed in advance is used for decoding. In addition, the encrypted inverse opals are chemically stable, providing invariant codes with high reproducibility. In addition, high mechanical stability enables the transfer of the films onto any surfaces. This novel encryption technology will provide a new opportunity in a wide range of security applications.     

Metallosupramolecular Photonic Elastomers with Self‐Healing Capability and Angle‐Independent Color

Photonic elastomers that can change colors like a chameleon have shown great promise in various applications. However, it still remains a challenge to produce artificial photonic elastomers with desired optical and mechanical properties. Here, the generation of metallosupramolecular polymer‐based photonic elastomers with tunable mechanical strength, angle‐independent structural color, and self‐healing capability is reported. The photonic elastomers are prepared by incorporating isotropically arranged monodispersed SiO₂ nanoparticles within a supramolecular elastomeric matrix based on metal coordination interaction between amino‐terminated poly(dimethylsiloxane) and cerium trichloride. The photonic elastomers exhibit angle‐independent structural colors, while Young's modulus and elongation at break of the as‐formed photonic elastomers reach 0.24 MPa and 150%, respectively. The superior elasticity of photonic elastomers enables their chameleon‐skin‐like mechanochromic capability. Moreover, the photonic elastomers are capable of healing scratches or cuts to ensure sustainable optical and mechanical properties, which is crucial to their applications in wearable devices, optical coating, and visualized force sensing.     

Single‐Stimulus‐Induced Modulation of Multiple Optical Properties

Stimuli‐responsive smart optical materials hold great promise for applications in active optics, display, sensing, energy conversion, military camouflage, and artificial intelligence. However, their applications are greatly restricted by the difficulty of tuning different optical properties within the same material, especially by a single stimulus. Here, magnetic modulations of multiple optical properties are demonstrated in a crystalline colloidal array (CCA) of magnetic nanorods. Small‐angle X‐ray scattering studies reveal that these nanorods form an unusual monoclinic crystal in concentrated suspensions. The CCA exhibits optical anisotropy in the form of a photonic bandgap and birefringence, thus enabling magnetic tuning of the structural color and transmittance at a rate of 50 Hz. As a proof‐of‐concept, it is further demonstrated that the fabrication of a multifunctional device for display, anticounterfeiting, and smart‐window applications based on this multiple magneto‐optical effect. The study not only provides a new model system for understanding colloidal assembly, but also opens up opportunities for new applications of smart optical materials for various purposes.     

Instantaneous,Simple, and Reversible Revealing of Invisible Patterns Encrypted in Robust Hollow Sphere Colloidal Photonic Crystals

The colors of photonic crystals are based on their periodic crystalline structure. They show clear advantages over conventional chromophores for many applications, mainly due to their anti‐photobleaching and responsiveness to stimuli. More specifically, combining colloidal photonic crystals and invisible patterns is important in steganography and watermarking for anticounterfeiting applications. Here a convenient way to imprint robust invisible patterns in colloidal crystals of hollow silica spheres is presented. While these patterns remain invisible under static environmental humidity, even up to near 100% relative humidity, they are unveiled immediately (≈100 ms) and fully reversibly by dynamic humid flow, e.g., human breath. They reveal themselves due to the extreme wettability of the patterned (etched) regions, as confirmed by contact angle measurements. The liquid surface tension threshold to induce wetting (revealing the imprinted invisible images) is evaluated by thermodynamic predictions and subsequently verified by exposure to various vapors with different surface tension. The color of the patterned regions is furthermore independently tuned by vapors with different refractive indices. Such a system can play a key role in applications such as anticounterfeiting, identification, and vapor sensing.     

Slow Photons for Photocatalysis and Photovoltaics

Solar light is widely recognized as one of the most valuable renewable energy sources for the future. However, the development of solar‐energy technologies is severely hindered by poor energy‐conversion efficiencies due to low optical‐absorption coefficients and low quantum‐conversion yield of current‐generation materials. Huge efforts have been devoted to investigating new strategies to improve the utilization of solar energy. Different chemical and physical strategies have been used to extend the spectral range or increase the conversion efficiency of materials, leading to very promising results. However, these methods have now begun to reach their limits. What is therefore the next big concept that could efficiently be used to enhance light harvesting? Despite its discovery many years ago, with the potential for becoming a powerful tool for enhanced light harvesting, the slow‐photon effect, a manifestation of light‐propagation control due to photonic structures, has largely been overlooked. This review presents theoretical as well as experimental progress on this effect, revealing that the photoreactivity of materials can be dramatically enhanced by exploiting slow photons. It is predicted that successful implementation of this strategy may open a very promising avenue for a broad spectrum of light‐energy‐conversion technologies.     

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.     

Dual Light and Temperature Responsive Micrometer‐Sized Structural Color Actuators

Externally induced color‐ and shape‐changes in micrometer‐sized objects are of great interest in novel application fields such as optofluidics and microrobotics. In this work, light and temperature responsive micrometer‐sized structural color actuators based on cholesteric liquid‐crystalline (CLC) polymer particles are presented. The particles are synthesized by suspension polymerization using a reactive CLC monomer mixture having a light responsive azobenzene dye. The particles exhibit anisotropic spot‐like and arc‐like reflective colored domains ranging from red to blue. Electron microscopy reveals a multidirectional asymmetric arrangement of the cholesteric layers in the particles and numerical simulations elucidate the anisotropic optical properties. Upon light exposure, the particles show reversible asymmetric shape deformations combined with structural color changes. When the temperature is increased above the liquid crystal‐isotropic phase transition temperature of the particles, the deformation is followed by a reduction or disappearance of the reflection. Such dual light and temperature responsive structural color actuators are interesting for a variety of micrometer‐sized devices.     

Engineering Gyroid‐Structured Functional Materials via Templates Discovered in Nature and in the Lab

In search of optimal structures for functional materials fabrication, the gyroid (G) structure has emerged as a promising subject of widespread research due to its distinct symmetry, 3D interconnected networks, and inherent chiral helices. In the past two decades, researchers have made great progress fabricating G‐structured functional materials (GSFMs) based on G templates discovered both in nature and in the lab. The GSFMs demonstrate extraordinary resonance when interacting with light and matter. The superior properties of GSFMs can be divided into two categories based on the dominant structural properties, namely, dramatic optical performances dominated by short‐range symmetry and well‐defined texture, and effective matter transport due to long‐range 3D interconnections and high integrity. In this review, G templates suitable for fabrication of GSFMs are summarized and classified. State‐of‐the‐art optical applications of GSFMs, including photonic bandgap materials, chiral devices, plasmonic materials, and matamaterials, are systematically discussed. Applications of GSFMs involved in effective electron transport and mass transport, including electronic devices, ultrafiltration, and catalysis, are highlighted. Existing challenges that may hinder the final application of GSFMS together with possible solutions are also presented.     

Tunable Photonic Microspheres of Comb‐Like Supramolecules

Photonic crystals (PCs) are ideal candidates for reflective color pigments with high color purity and brightness due to tunable optical stop band. Herein, the generation of PC microspheres through 3D confined supramolecular assembly of block copolymers (polystyrene‐block‐poly(2‐vinylpyridine), PS‐b‐P2VP) and small molecules (3‐n‐pentadecylphenol, PDP) in emulsion droplets is demonstrated. The intrinsic structural colors of the PC microspheres are effectively regulated by tuning hydrogen‐bonding interaction between P2VP blocks and PDP, where reflected color can be readily tuned across the whole visible spectrum range. Also, the effects of both PDP and homopolymer (hPS) on periodic structure and optical properties of the microspheres are investigated. Moreover, the spectral results of finite element method (FEM) simulation agree well with the variation of structural colors by tuning the periodicity in PC microspheres. The supramolecular microspheres with tunable intrinsic structural color can be potentially useful in the various practical applications including display, anti‐counterfeit printing and painting.     

Controlling the Photonic Properties of Cholesteric Cellulose Nanocrystal Films with Magnets

The self‐assembly of cellulose nanocrystals is a powerful method for the fabrication of biosourced photonic films with a chiral optical response. While various techniques have been exploited to tune the optical properties of such systems, the presence of external fields has yet to be reported to significantly modify their optical properties. In this work, by using small commercial magnets (≈ 0.5–1.2 T) the orientation of the cholesteric domains is enabled to tune in suspension as they assemble into films. A detailed analysis of these films shows an unprecedented control of their angular response. This simple and yet powerful technique unlocks new possibilities in designing the visual appearance of such iridescent films, ranging from metallic to pixelated or matt textures, paving the way for the development of truly sustainable photonic pigments in coatings, cosmetics, and security labeling.     

Self‐Assembled Photonic Structures

Photonic crystals have proven their potential and are nowadays a familiar concept. They have been approached from many scientific and technological flanks. Among the many techniques devised to implement this technology self‐assembly has always been one of great popularity surely due to its ease of access and the richness of results offered. Self‐assembly is also probably the approach entailing more materials aspects owing to the fact that they lend themselves to be fabricated by a great many, very different methods on a vast variety of materials and to multiple purposes. To these well‐known material systems a new sibling has been born (photonic glass) expanding the paradigm of optical materials inspired by solid state physics crystal concept. It is expected that they may become an important player in the near future not only because they complement the properties of photonic crystals but because they entice the researchers’ curiosity. In this review a panorama is presented of the state of the art in this field with the view to serve a broad community concerned with materials aspects of photonic structures and more so those interested in self‐assembly.     

Mechanochromic Photonic Gels

Polymer gels are remarkable materials with physical structures that can adapt significantly and quite rapidly with changes in the local environment, such as temperature, light intensity, electrochemistry, and mechanical force. An interesting phenomenon observed in certain polymer gel systems is mechanochromism – a change in color due to a mechanical deformation. Mechanochromic photonic gels are periodically structured gels engineered with a photonic stopband that can be tuned by mechanical forces to reflect specific colors. These materials have potential as mechanochromic sensors because both the mechanical and optical properties are highly tailorable via incorporation of diluents, solvents, nanoparticles, or polymers, or the application of stimuli such as temperature, pH, or electric or strain fields. Recent advances in photonic gels that display strain‐dependent optical properties are discussed. In particular, this discussion focuses primarily on polymer‐based photonic gels that are directly or indirectly fabricated via self‐assembly, as these materials are promising soft material platforms for scalable mechanochromic sensors.     

3D Helix Engineering in Chiral Photonic Materials

Engineering the helical structure of chiral photonic materials in three dimensions remains a challenge. 3D helix engineered photonic materials are fabricated by local stratification in a photopolymerizable chiral nematic liquid crystal. The obtained chiral photonic materials reflect both handedness of circular polarized light and show super‐reflectivity. Simulations match the experimentally observed photonic properties and reveal a distorted helical structure. 3D engineered polymer films can be made that reflect both left‐ and right handed circular and linear polarized light dependent and exhibit a changing color contrast upon altering the polarization of incident light. Hence, these 3D engineered photonic materials are of interest for new and emerging applications ranging from anti‐counterfeit labels and data encryption to aesthetics and super‐reflective films.     

Chiroptical Nanocellulose Bio-Labels for Independent Multi-Channel Optical Encryption

Advanced multiplexing optical labels with multiple information channels provide a powerful strategy for large-capacity and high-security information encryption. However, current optical labels face challenges of difficulty to realize independent multi-channel encryption, cumbersome design, and environmental pollution. Herein, multiplexing chiroptical bio-labels integrating with multiple optical elements, including structural color, photoluminescence (PL), circular polarized light activity, humidity-responsible color, and micro/nano physical patterns, are constructed in complex design based on host-guest self-assembly of cellulose nanocrystals and bio-gold nanoclusters. The thin nanocellulose labels exhibit tunable circular polarized structural color crossover the entire visible wavelength and circularly polarized PL with the highest-recorded dissymmetry factor up to 1.05 due to the well-ordered chiral organization of templated gold nanoclusters. Most importantly, these elements can independently encode customized anti-counterfeiting information to achieve five independent channels of high-level anti-counterfeiting, which are rarely achieved in traditional materials and design counterparts. Considering the exceptional seamless integration of five independent encryption channels and the recyclable features of labels, the bio-labels have great potential for the next generation anti-counterfeiting materials technology.     

Single Nanoparticle Detection Using Optical Microcavities

Detection of nanoscale objects is highly desirable in various fields such as early‐stage disease diagnosis, environmental monitoring and homeland security. Optical microcavity sensors are renowned for ultrahigh sensitivities due to strongly enhanced light‐matter interaction. This review focuses on single nanoparticle detection using optical whispering gallery microcavities and photonic crystal microcavities, both of which have been developing rapidly over the past few years. The reactive and dissipative sensing methods, characterized by light‐analyte interactions, are explained explicitly. The sensitivity and the detection limit are essentially determined by the cavity properties, and are limited by the various noise sources in the measurements. On the one hand, recent advances include significant sensitivity enhancement using techniques to construct novel microcavity structures with reduced mode volumes, to localize the mode field, or to introduce optical gain. On the other hand, researchers attempt to lower the detection limit by improving the spectral resolution, which can be implemented by suppressing the experimental noises. We also review the methods of achieving a better temporal resolution by employing mode locking techniques or cavity ring up spectroscopy. In conclusion, outlooks on the possible ways to implement microcavity‐based sensing devices and potential applications are provided.