Photonic Pigments Research Articles

Carbon dot-loaded Fe3O4 as photonic pigments for multilevel anti-counterfeiting

Amorphous arrays assembled from colloidal microspheres are a way that obtains angle-independent structural colors. In order to obtain additional properties, colloidal microspheres, which are constituent units, can be modified with other materials. Here, we utilized the silane-functionalized carbon quantum dots (SiCDs) by incorporating them into the Stöber reaction to fabricate Fe3O4@SiO2/SiCDs nanospheres with a core-shell structure. Amorphous colloidal arrays (ACAs) were constructed on commercial printing paper using Fe3O4@SiO2/SiCDs nanoparticles as structural units by a simple permeation assembly. Macroscopically, the prepared ACAs exhibit the magnetic properties of Fe3O4, while under sunlight, they display bright, angle-independent structural colors. Under ultraviolet light, the array shows significant fluorescence. This enables the presentation of multidimensional information under varying magnetic and lighting conditions. By adjusting the thickness of the outer SiO2/SiCDs composite layer, the optical properties and magnetism can be controlled easily. Moreover, due to the strong light absorption capability and high refractive index of Fe3O4, the digital patterns constructed with Fe3O4@SiO2/SiCDs nanospheres demonstrate excellent multi-level anti-counterfeiting characteristics, even under water exposure. The magnetic properties of Fe3O4@SiO2/SiCDs nanospheres, along with their distinct display characteristics under different optical environments, suggest their wide applicability in the fields of multifunctional anti-counterfeiting pigments, bioimaging, and sensing displays.

Host-Guest Interaction Mediated Interfacial Co-Assembly of Cyclodextrin and Bottlebrush Surfactants for Precisely Tunable Photonic Supraballs.

Investigations of host-guest interactions at water-oil (w/o) interfaces are limited in single emulsion systems producing simple self-assembled objects with limited uses. Here, within hierarchically ordered water-in-oil-in-water (w/o/w) multiple emulsion droplets, interfacial self-assembly of (polynorbornene-graft-polystyrene)-block-(polynorbornene-graft-polyethylene glycol) (PNPS-b-PNPEG) bottlebrush block copolymers can be precisely controlled through host-guest interactions. α-Cyclodextrin (α-CD) in the aqueous phase can thread onto PEG side chains of the bottlebrush surfactants adsorbed at the w/o interface, leading to dehydration and collapsed chain conformation of the PEG block. Consequently, spherical curvature of the w/o internal droplets increases with the increased asymmetry of the bottlebrush molecules, producing photonic supraballs with precisely tailored structural parameters as well as photonic bandgaps. This work provides a simple but highly effective strategy for precise manipulation of complex emulsion systems applicable in a variety of applications, such as photonic pigments, cosmetic products, pesticides, artificial cells, etc.

Photonic Pigments of Polystyrene-block-Polyvinylpyrrolidone Bottlebrush Block Copolymers via Sustainable Organized Spontaneous Emulsification.

Prior studies on photonic pigments of amphiphilic bottlebrush block copolymers (BBCPs) through an organized spontaneous emulsification (OSE) mechanism have been limited to using polyethylene glycol (PEG) as the hydrophilic side chains and toluene as the organic phase. Herein, a family of polystyrene-block-polyvinylpyrrolidone (PS-b-PVP) BBCPs are synthesized with PVP as the hydrophilic block. Biocompatible and sustainable anisole is employed for dissolving the obtained BBCPs followed by emulsification of the solutions in water. Subsequent evaporation of oil-in-water emulsion droplets triggers the OSE mechanism, producing thermodynamically stable water-in-oil-in-water (w/o/w) multiple emulsions with uniform and closely packed internal droplet arrays through the assembly of the BBCPs at the w/o interface. Upon solidification, the homogeneous porous structures are formed within the photonic microparticles that exhibit visible structural colors. The pore diameter is widely tunable (150∼314 nm) by changing the degree of polymerization of BBCP (69∼110), resulting in tunable colors across the whole visible spectrum. This work demonstrates useful knowledge that OSE can be generally used in the fabrication of ordered porous materials with tunable internal functional groups, not only for photonic applications, but also offers a potential platform for catalysis, sensing, separation, encapsulation, etc.

Recent Advances in 1D Photonic Crystals: Diverse Morphologies and Distinctive Structural Colors for Multifaceted Applications

Abstract1D photonic crystals (1DPCs) with hierarchically structured lamellar periodic frameworks that enable precise control of light‐matter interactions and contribute robust structural colors represent a groundbreaking advancement in optical materials. The microstructural characteristics and the constituent material properties of these photonic materials play pivotal roles in determining their optical performance and functionality. In recent years, a diverse array of novel 1D photonic structures crafted from various materials emerged, showcasing their tremendous potential in advanced applications. This article provides an in‐depth review of the recent developments in 1DPCs, emphasizing their morphological designs, fabrication strategies, and optical applications. In detail, 1DPCs featuring distinct geometrical morphologies, including lamellar, helical, fibrous, spherical, and nanochained structures are systematically introduced, highlighting the unique optical properties arising from their periodic microstructures. Then, various fabrication methods, involving some innovative techniques utilizing standing‐wave optics, UV dual photopolymerization, and inkjet printing, are succinctly summarized for constructing different photonic structures by using diverse building materials. Subsequently, some typical application examples of 1D photonic materials are listed and discussed involving visual sensing, intelligent displays, anti‐counterfeiting technology, photonic pigments, and optical devices. Finally, the passage addresses the current challenges and presents a forward‐looking perspective on the future fabrication and application of 1DPCs.

Waterborne Polymer Coatings with Bright Noniridescent Structural Colors.

Structural color pigments offer an efficient, sustainable, and environmentally friendly approach to obtain waterborne polymer coatings. We developed polymer-based spherical photonic pigments to incorporate in aqueous dispersions of polymer nanoparticles used to obtain waterborne polymer films. Our spherical photonic pigments are assembled from polymer nanoparticles and are highly stable in water dispersion, maintaining their optical properties in the final polymer films. Unlike conventional dyes and pigments, which are prone to photobleaching because they are based on the absorption of light, photonic pigments rely on the selective reflection of light by their nanostructure and therefore are not photodegraded. Furthermore, different colors can be obtained from the same materials, changing only their nanostructure, in this case, the size of the polymer nanoparticles. Our novel spherical photonic pigments are noniridescent and can be incorporated in aqueous polymer nanoparticle dispersions without deteriorating their structure to produce waterborne polymer coatings with structural color. This approach for structural colored waterborne polymer coatings is efficient, simple, and environmentally friendly, offering excellent prospects for application in paints and coatings.

C-Dot-Embedded SiO2 Concentric Microspheres for Bright Fluorescent Photonic Pigments.

A simple yet powerful approach to obtain structural color is the amorphous assembly of colloidal spheres, which is also referred to as the amorphous photonic structure or photonic glasses (PGs). Additionally, the functionalization of the colloidal spheres as building blocks can further endow the resulting PGs with multifunctions. Herein, we have developed a facile strategy to prepare SiO2 colloidal spheres with concentrically embedded carbon dots (CDs). Notably, the CDs are prepared and silane-functionalized simultaneously, which enables the perfect incorporation of CDs into the Si-O network during the Stöber reaction and thus leads to the formation of a concentric SiO2/CD interlayer within the obtained SiO2 spheres. Moreover, the obtained SiO2/CD spheres can be applied as photonic pigments by assembling them into PGs, which exhibit structural color under daylight and fluorescence under UV illumination. With incorporation of carbon black, the structural color saturation and fluorescence intensity can be further manipulated. Owing to the combination of structural colored PGs and fluorescent CDs, our study can offer inspiration for color- and fluorescence-related applications such as sensing, in vivo imaging, LEDs, and anticounterfeiting.

Eco-friendly cellulosic photonic pigments with tunable structural color for anti-counterfeiting and decorative applications

Cholesteric cellulose films exhibiting an adjustable reflection wavelength across the entire visible range were obtained through the application of ultrasound treatment to a suspension of cellulose nanocrystals (CNCs) prior to casting. The influence of both low and high intensity ultrasound power on the structural color of iridescent films was systematically investigated, along with an elucidation of the mechanism behind helical pitch regulation. The findings reveal that low ultrasonic power applied to the CNC suspension has minimal impact on the structural color of the CNC film, primarily enhancing the dispersion of CNC. On the other hand, high ultrasonic power applied to the CNC suspension can effectively adjust the structural color thanks to not only improving the dispersion of CNCs suspensions, but also altering the morphology and size of the CNCs. More importantly, co-friendly cellulosic photonic pigments with tunable structural color can be easily obtained utilizing the fragility of iridescent films for applications such as anti-counterfeiting labels, nail modification and decorative coatings and so on, thereby demonstrating considerable potential for practical utilization.

Hierarchically Structured Deformation‐Sensing Mechanochromic Pigments

Mechanochromic materials alter their color in response to mechanical force and are useful for both fundamental studies and practical applications. Several approaches are used to render polymers mechanochromic, but they generally suffer from limitations in sensing range, capacity to provide quantitative information, and their capability to enable broad and simple implementation. Here, is it reported that these problems can be overcome by combining photonic structures, which alter their reflection upon deformation, with covalent mechanophores, whose spectral properties change upon mechanically induced bond scission, in hierarchically structured mechanochromic pigments. This is achieved by synthesizing microspheres consisting of an elastic polymer with spiropyran-based cross-links and non-close-packed silica nanoparticles. A strain of less than 1% can be detected in a shift of the reflection band from the photonic structure, while the onset strain for the conversion of the spiropyran into fluorescent merocyanine ranges from 30% to 70%, creating a broad strain detection range. The two responses are tailorable and synergistic, permitting the activation strain for the mechanophore response to be tuned. The mechano-sensing photonic pigments are demonstrated to be readily incorporated into different polymeric materials of interest and quantitatively probe spatially heterogeneous deformations over a large strain range.

Robust Full-Spectral Color Tuning of Photonic Colloids.

Creation of color through photonic morphologies manufactured by molecular self-assembly is a promising approach, but the complexity and lack of robustness of the fabrication processes have limited their technical exploitation. Here, it is shown that photonic spheres with full-color tuning across the entire visible spectrum can be readily and reliably achieved by the emulsification of solutions containing a block copolymer (BCP) and two swelling additives. Solvent diffusion out of the emulsion droplets gives rise to 20-150µm-sized spheres with an onion-like lamellar morphology. Controlling the lamellar thickness by differential swelling with the two additives enables color tuning of the Bragg interference-based reflection band across the entire visible spectrum. By studying five different systems, a set of important principles for manufacturing photonic colloids is established. Two swelling additives are required, one of which must exhibit strong interactions with one of the BCP blocks. The additives should be chosen to enhance the dielectric contrast, and the formation kinetics of the spheres must be sufficiently slow to enable the emergence of the photonic morphology. The proposed approach is versatile and robust and allows the scalable production of photonic pigments with possible future applications in inks for cosmetics and arts, coatings, and displays.

Block Copolymer-based Photonic Pigments: Towards Structural Non-iridescent Brilliant Coloration

Creating color through the self-assembly of specific building blocks to fabricate photonic morphologies is a promising and intriguing approach to reproducing the flamboyant visual effects and dynamic properties observed in the natural world. However, the complexity and lack of robustness in the manufacture of these nanostructured materials hinder their technical exploitation on a large scale. To overcome such limitations, here we present a novel methodology to create bioinspired photonic pigments as dispersed and micrometer-scale particles based on highly ordered concentric lamellar microspheres made of block copolymers. First, we introduce the fabrication protocol and the advantages of this approach compared to the traditional colloidal self-assembly. Then, we discuss some possible future research directions focused on developing hybrid organic-inorganic photonic pigments with enhanced dielectric contrast, reduced scattering, and specific functionalities. Finally, we speculate on possible applications for these structures that go beyond their use as simple photonic pigments.

Precisely Tunable Photonic Pigments via Interfacial Self-Assembly of Bottlebrush Block Copolymer Binary Blends

Precisely Tunable Photonic Pigments via Interfacial Self-Assembly of Bottlebrush Block Copolymer Binary Blends

Deconvoluting the Optical Response of Biocompatible Photonic Pigments.

To unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response. A library of photonic pigments is produced from poly(norbornene‐graft‐polycaprolactone)‐block‐poly(norbornene‐graft‐polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure–optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite‐difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.

Deconvoluting the Optical Response of Biocompatible Photonic Pigments.

To unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response. A library of photonic pigments is produced from poly(norbornene-graft-polycaprolactone)-block-poly(norbornene-graft-polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure-optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite-difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.

Precise Tailoring of Polyester Bottlebrush Amphiphiles toward Eco‐Friendly Photonic Pigments via Interfacial Self‐Assembly

AbstractBiodegradable photonic microspheres with structural colors are promising substitutes to polluting microbeads and toxic dyes. Here, amphiphilic polyester‐block‐poly(ethylene glycol) bottlebrush block copolymers (BBCPs) with polylactic acid or poly(ϵ‐caprolactone) as the hydrophobic block are synthesized and used to fabricate eco‐friendly photonic pigments. Molecular parameters of BBCPs, including rigidity and symmetry, are precisely tailored by variation of side chain lengths, which enables effective manipulation of interfacial tension (γ). Organized spontaneous emulsion mechanism is enabled only whenγfalls in a suitable range (10.6–14.3 mN m−1), producing ordered water‐in‐oil‐in‐water multiple emulsions and ordered porous structures. Consequently, highly saturated and tunable structural colors are observed due to coherent light scattering from the porous structures. Such photonic materials are nontoxic as confirmed by careful safety tests using aquatic model organisms.

Precise Tailoring of Polyester Bottlebrush Amphiphiles toward Eco-Friendly Photonic Pigments via Interfacial Self-Assembly.

Biodegradable photonic microspheres with structural colors are promising substitutes to polluting microbeads and toxic dyes. Here, amphiphilic polyester-block-poly(ethylene glycol) bottlebrush block copolymers (BBCPs) with polylactic acid or poly(ϵ-caprolactone) as the hydrophobic block are synthesized and used to fabricate eco-friendly photonic pigments. Molecular parameters of BBCPs, including rigidity and symmetry, are precisely tailored by variation of side chain lengths, which enables effective manipulation of interfacial tension (γ). Organized spontaneous emulsion mechanism is enabled only when γ falls in a suitable range (10.6-14.3 mN m-1 ), producing ordered water-in-oil-in-water multiple emulsions and ordered porous structures. Consequently, highly saturated and tunable structural colors are observed due to coherent light scattering from the porous structures. Such photonic materials are nontoxic as confirmed by careful safety tests using aquatic model organisms.

Cellulose photonic pigments

When pursuing sustainable approaches to fabricate photonic structures, nature can be used as a source of inspiration for both the nanoarchitecture and the constituent materials. Although several biomaterials have been promised as suitable candidates for photonic materials and pigments, their fabrication processes have been limited to the small to medium-scale production of films. Here, by employing a substrate-free process, structurally coloured microparticles are produced via the confined self-assembly of a cholesteric cellulose nanocrystal (CNC) suspension within emulsified microdroplets. Upon drying, the droplets undergo multiple buckling events, which allow for greater contraction of the nanostructure than predicted for a spherical geometry. This buckling, combined with a solvent or thermal post-treatment, enables the production of dispersions of vibrant red, green, and blue cellulose photonic pigments. The hierarchical structure of these pigments enables the deposition of coatings with angular independent colour, offering a consistent visual appearance across a wide range of viewing angles.

The Limited Palette for Photonic Block-Copolymer Materials: A Historical Problem or a Practical Limitation?

Block-copolymer self-assembly has proven to be an effective route for the fabrication of photonic films and, more recently, photonic pigments. However, despite extensive research on this topic over the past two decades, the palette of monomers and polymers employed to produce such structurally colored materials has remained surprisingly limited. In this Scientific Perspective, the commonly used block-copolymer systems reported in the literature are summarized (considering both linear and brush architectures) and their use is rationalized from the point of view of both their historical development and physicochemical constraints. Finally, the current challenges facing the field are discussed and promising new areas of research are highlighted to inspire the community to pursue new directions.

The Limited Palette for Photonic Block-Copolymer Materials: A Historical Problem or a Practical Limitation?

Block‐copolymer self‐assembly has proven to be an effective route for the fabrication of photonic films and, more recently, photonic pigments. However, despite extensive research on this topic over the past two decades, the palette of monomers and polymers employed to produce such structurally colored materials has remained surprisingly limited. In this Scientific Perspective, the commonly used block‐copolymer systems reported in the literature are summarized (considering both linear and brush architectures) and their use is rationalized from the point of view of both their historical development and physicochemical constraints. Finally, the current challenges facing the field are discussed and promising new areas of research are highlighted to inspire the community to pursue new directions.

Spherical colloidal photonic pigments with saturated structural colors through temperature-controlled polymer nanoparticle assembly

Structural color is based on the reflection of light by materials with a periodic variation of refractive index in the length scale of the wavelength of visible light. Unlike conventional dyes and pigments, there is no absorption of radiation, and therefore structural pigments are impervious to fading by photobleaching. Also, because structural color is mainly dependent on structure, not composition, it can be obtained from materials with low environmental impact and toxicity. Structural pigments with colors covering the full visible spectrum can therefore be obtained from the same colloidal materials, by tuning only their size and the spatial arrangement of individual nanoparticles.Here, we show that using polymer nanoparticles with low size dispersity, and controlling the kinetics and the inter-particle interactions during the assembly process, one can obtain spherical non-iridescent photonic pigment. Using polymer nanoparticles with diameters in the range of 170 nm–330 nm, we obtain structural pigments with bright colors spanning the full visible spectrum, with different hue and saturation. The optical properties of these pigments are directly related to the arrangement of the polymer nanoparticles within the spherical structural pigment. This arrangement, controlled by the surface charge of the nanoparticles and the rate of water evaporation from the template droplets containing the nanoparticles, changes from an ordered face-centered cubic packing at 50 °C, to an almost amorphous packing at 65 °C. Our spherical photonic pigments reflect a plethora of vibrant colors with low angle dependence, with excellent prospects for used as dispersible pigments in the development of environmentally friendly coatings with non-fading color.

Multicolor Photonic Pigments for Rotation‐Asymmetric Mechanochromic Devices (Adv. Mater. 4/2022)

Photonic Pigments In article number 2107398, Yadong Yin and co-workers highlight the integration of magnetically responsive photonic pigments with orientation-dependent structural colors into optoelectronic devices that can exhibit dynamic color-switching or display predesigned patterns upon simple rotation. Such photonic pigments are promising materials in the development of high-performance sensors, color displays, rewritable papers, and anti-counterfeiting devices.