Photonic Films Research Articles

Direct Ink Writing of Rigid Microparticles.

Direct ink writing (DIW) enables 3D printing of macroscopic objects with well-defined structures and compositions that controllably change over length scales of order 100 µm. Unfortunately, only a limited number of materials can be processed through DIW because it imparts stringent rheological requirements on inks. This limitation can be overcome for soft materials, if they are formulated as microparticles that, if jammed, fulfill the rheological requirements to be printed. By contrast, densely packed rigid microparticles with stiffnesses exceeding 2 MPa do not exhibit appropriate rheological properties that enable DIW. Here, an ink composed of up to 60 vol% rigid microparticles with core stiffnesses up to 50 MPa is introduced. To achieve this goal, rigid microparticles possessing soft hydrogel shells are produced. The 3D printed fragile granular structure is transformed into a load-bearing granular material through the formation of a 2nd network within the soft shells and in the interstitial spaces. The potential of these particles is demonstrated to be printed into intricate 3D structures, such as a trophy cup, or cast into flexible macroscopic photonic films.

Programmable Robotic Shape Shifting and Color Morphing Dynamics Through Magneto-Mechano-Chromic Coupling.

Recreating natural organisms' dynamic shape-morphing and adaptive color-changing capabilities in a compact structure poses significant challenges but unlocks unprecedented hybridized robotic-visual applications. Overcoming programmability and predictability obstacles is key to achieving real-time, responsive changes in appearance and functionality, enhancing robot-environment-user interactions in ways previously unattainable. Herein, a Soft Magneto-Mechano-Chromic (SoMMeC) structure comprising a magnetic actuating and a synthetic photonic film, mirroring the intricate color-tuning mechanism of chameleons is devised. A model combining numerical simulation and a strain-dependent color evolution map enables precise predictions and controllable shape-color alterations across various geometrical and magnetization profiles. The SoMMeC exhibits rapid (0.1s), broad (full-visible spectrum), tether-free (remote magnetic manipulation), and programmable (model-guided control) color transformations, surpassing traditional limitations with its real-time response, broad and omnidirectional coloration for enhanced visibility, and robustness against external disturbances. The SoMMeC translates into dynamic advertising iridescence, adaptive camouflage, self-sensing, and multi-level encryption, and transcends traditional robotics by seamlessly blending dynamic movement with nuanced visual changes. It opens up a spectrum of applications that redefine robotic functionality through dynamic appearance modulation, making robotic systems more versatile, adaptive, and suitable for unexplored integrative functions.

A multifunctional and tough lotus root starch-based bio-photonic hydrogel for stretchable fabric pattern color change and water rewriting.

Photonic crystal hydrogels (PCHs) are innovative materials that translate imperceptible deformations and humidity changes into visible colors, broadening the applications of photonics in bioengineering and smart materials. To overcome poor mechanical properties of traditional PCHs limited by weak intermolecular forces, we designed a PCH with a dual-network framework comprising N-isopropylacrylamide-co-acrylamide (NIPAM-co-AM) and biomass lotus root starch (LR). Since LR is rich in hydroxyl groups, it can undergo molecular linkage entanglement with the NIPAM-co-AM hydrogel matrix, forming hydrogen bonds that significantly enhance the mechanical properties of the PCH. We have prepared PCH films capable of conveying multidimensional information about the extent and distribution of transient deformation by encapsulating magnetic photonic crystal microspheres (MPCMs) within a hydrogel matrix. The PCH films were found to have ultrafast response time (< 10 s), full-color tunable range, high spatial resolution, excellent mechanical toughness (tensile up to 0.17 MPa) and sensitivity (2.52 nm %-1), and were able to sense relative humidity (RH) from 11 % to 98 %. Equipped with a dynamically reconfigurable lattice, this dual-responsive (tensile/humidity) PCH not only facilitates the creation of water-rewritable photonic films but also holds promise for integration into structural color elastic fabrics, thereby presenting novel prospects for smart textile applications.

Spontaneously-Oriented Evaporated Organic Semiconductor Thin Films for Second-Order Nonlinear Photonics

Spontaneously-Oriented Evaporated Organic Semiconductor Thin Films for Second-Order Nonlinear Photonics

Porous cellulose photonic film via controlled unidirectional interlayer freezing for rapid visual sensing

Structure color, arising from the interaction of light with regularly arranged sub-micrometer-sized structures, has spurred interest in sensor design. However, typical cellulose nanocrystal (CNC) photonic films derived from biomass, known for their sustainability and cost-effectiveness, often suffer from limited sensitivity and slow response times due to their dense structure. To address this challenge, we have utilized a unidirectional interlayer freezing-photopolymerization strategy to introduce porous structures into CNC photonic films without compromising their vibrant structural color. This method harnesses ice crystal-induced lamellar pores while preserving the periodic arrangement of CNCs. The underlying mechanism of ice kinetics and CNC assembly is established, highlighting the transition from non-iridescent aerogels to iridescent, porous photonic films. The resulting porous CNC photonic film exhibits apparent color response and rapid sensing capabilities in response to various solvent stimuli, outperforming its non-porous counterparts. We have validated the film as a portable vapor detector for rapid visualized alcohol detection. This approach provides promising developments in sustainable, highly responsive sensor technologies.

Bioinspired transparent ultratough birefringent photonic films with engineerable interference colors derived from in-situ synthesis of CaCO3

Chameleons can rapidly modify their coloration by manipulating the arrangement of iridophores encompassing guanine crystals in their dermis, which enables incident light to undergo birefringence. Various biomaterials have been designed to mimic the arrangement of guanine crystals, yet instances of synthesizing bottom-up structures with anisotropy for optical functionality remain rare. In this study, we report a novel two-step gas diffusion method for in-situ synthesis of CaCO3 (Vaterite) within a hydrogel to fabricate a bio-photonic film displaying birefringence interference colors. This strategy enables the successful fabrication of an inorganic–organic photonic film with superior mechanical properties and flexibility, resulting in high transparency, superior toughness, and adjustable optical anisotropy. Through a combination of experiment and simulation results, we elucidated the critical role played by shape factor (distribution) and structural factor (particle size) in producing transmitted interference colors. Finally, the birefringent photonic films prepared using the dot-plate method can function as optical patterns accurately representing the “on”/“off” state within a binary system. This system offers high spatial resolution, excellent repeatability, and precise controllability of optical properties, making it applicable in fields such as information encryption and decrytion. Our study has successfully synthesized photonic material with anisotropic structure though in-situ method while elucidating the underlying mechanism governing their ability to generate transmission interference colors, thus opening up new avenues for transparent flexible polarized optics, imperceptible wearable devices, and advanced information encryption.

Phase change polymer-based structural color photonic films for contactless and inkless writing irreversibly

Thermal-responsive photonic crystals (PCs) have attracted considerable interest due to their triggerable and adjustable optical capabilities, which are promising for various applications. However, developing a mechanism for rapid and irreversible structural color transformation in PCs that enables contactless and inkless writing has significant research value. Herein, phase change polymers are incorporated into functional optical platforms capable of rapid and irreversible structural color transformation in response to thermal stimuli. In crystalline state, phase change polymers used as inverse opal scaffolds in photonic films produce structural color with high saturation. The collapse of the highly ordered inverse opal structure, driven by thermal-mediated transformation during the crystalline/amorphous conversion of phase change polymers, is identified as the primary mechanism for achieving rapid and irreversible structural color transformation. These significant color variations between the inverse opal and collapsed structures provide high color contrast and resolution. The photonic films exhibit excellent hydrophobicity, solvent resistance, and storage stability. Additionally, incorporating the photothermal material carbon black (CB) enhances color saturation and imparts efficient photothermal conversion ability to films. By modulating the photothermal effect via near-infrared (NIR) laser light, phase change polymer-based structural color photonic films can achieve a permanent configuration at 42 °C, resulting in high-resolution images. These outstanding features offer a feasible method for next-generation innovative inkless writing and printing.

Pyramid Textured Photonic Films with High-Refractive Index Fillers for Efficient Radiative Cooling.

Sub-ambient cooling technologies relying on passive radiation have garnered escalating research attention owing to the challenges posed by global warming and substantial energy consumption inherent in active cooling systems. However, achieving highly efficient radiative cooling devices capable of effective heat dissipation remains a challenge. Herein, by synergic optimization of the micro-pyramid surface structures and 2D hexagonal boron nitride nanoplates (h-BNNs) scattering fillers, pyramid textured photonic films with remarkable solar reflectivity of 98.5% and a mid-infrared (MIR) emittance of 97.2% are presented. The h-BNNs scattering filler with high thermal conductivity contributed to the enhanced through-plane thermal conductivity up to 0.496W m-1 K-1 and the in-plane thermal conductivity of 3.175W m-1 K-1. The photonic films exhibit an optimized effective radiative cooling power of 201.2W m-2 at 40°C under a solar irradiance of 900W m-2 and a daily sub-ambient cooling effect up to 11°C. Even with simultaneous internal heat generation by a 10W ceramic heater and external solar irradiance of 500W m-2, a sub-ambient cooling of 5°C can be realized. The synergic matching strategy of high thermal conductivity scattering fillers and microstructured photonic surfaces holds promise for scalablesub-ambient radiative cooling technologies.

All‐Cellulose‐Based Flexible Photonic Films

AbstractCellulose nanocrystals (CNCs) are environmentally friendly building blocks used in the preparation of chiral nematic iridescent films through evaporation‐induced self‐assembly. However, the brittleness of CNC films limits their versatility, especially in applications that require mechanical flexibility. In this study, it is innovatively engineered flexible colored CNC films entirely composed of cellulose by introducing cross‐linked chemically modified cellulose nanofibers (CNFs) as a supporting network. By reducing the surface charge content of CNFs and anchoring them in a network, the disruption to the self‐assembly process of CNCs caused by CNFs is minimized. This effectively preserves the structural colors of CNCs films. Furthermore, the CNFs network enhances the tensile strength and elongation of these all‐cellulose composite films, enabling them to be folded with excellent flexibility while still maintaining a high Young's modulus. Vibrant red, green, and blue‐colored all‐cellulose photonic films can also be achieved by simply adjusting the sonication energy input on the suspension of CNCs. The all‐cellulose‐based flexible films have the potential to be applied as an eco‐friendly and sustainable photonic material when flexibility is essential, for instance, in applications like flexible sensors, anti‐counterfeit labels, or foldable display components.

Laser‐Inscribable, Moisture‐Responsive Cellulosic Supramolecular Structures with Tunable Broadband Coloration

AbstractAdaptive photonic films in response to external stimuli have broad applications in optical communications, sensing, and anticounterfeiting. Yet, it remains challenging to develop photonic structures with tailorable fine patterns that display broadband color changing under ambient conditions. Here a hydrogen‐bonded supramolecular cholesteric liquid crystalline polymer (CLCP) that is mediated by a binary solvent consisting of citric acid (CA) and water is presented. The incorporation of CA not only improves the long‐range order of CLCPs through evaporation‐induced self‐assembly but is also capable of tuning their helical pitch across the entire visible spectrum. The extent of hydration‐induced pitch expansion can be further manipulated by thermal crosslinking, enabling a unique patterning strategy based on mask‐free, programmable laser inscription. High‐precision photonic patterns are created onto CLCPs, which reveal themselves upon hydration in high visual contrast. The study offers a feasible and up‐scaling route toward tailoring environmentally adaptive CLCPs with tunable broadband coloration and highly programmable photonic patterns.

Cellulose Metamaterials with Hetero‐Profiled Topology via Structure Rearrangement During Ball Milling for Daytime Radiative Cooling

AbstractPassive radiative cooling is a zero‐energy consumption approach, which can dissipate heat to outer space by emitting infrared radiation through the transparency window. Traditional cooling materials, such as photonic films, metafabrics, and polymer foams, still suffer from complex preparation processes and high costs. In this work, it is reported that natural cellulose can be converted into a “green” optical metamaterial by rational structure reconfiguration at the micro/nano level via scalable ball milling technology for efficient daytime radiative cooling. Specifically, fine‐tuning the shearing kinetics in the mechanochemistry process, cellulosic optical metamaterial (COM) with ≈98% solar reflectivity and ≈0.97 infrared emissivity has been successfully achieved, which can break through the theoretical value of photonic crystals as well as the conventional synthetic optical materials. The COMSOL simulation reveals that the excellent optical properties of the cellulose metamaterial are explained by the “confined scattering” effect caused by the rearranged heterostructure at the micro/nano level. Outdoor tests demonstrat that the COM‐based coating exhibits a daytime radiative cooling efficiency of 5.7 °C in hot Nanjing. Meanwhile, the COM can be produced into different scattering materials via spray coating, freeze casting, and solution casting technology. This study will facilitate the development of scalable and sustainable optical metamaterials for mitigating energy consumption.

Near-Infrared Circularly Polarized Luminescent Physical Unclonable Functions.

Distinguished from traditional physical unclonable functions (PUFs), optical PUFs derive their encoded information from the optical properties of materials, offering distinct advantages, including solution processability, material versatility, and tunable luminescence performance. However, existing research on optical PUFs has predominantly centered on visible photoluminescence, while advanced optical PUFs based on higher-level covert light remain unexplored. In this study, we present optical PUFs based on the utilization of the covert light of near-infrared circularly polarized luminescence (NIR-CPL). This interesting property is achieved by incorporating Yb-doped metal halide perovskite nanocrystals (Yb-PeNCs) possessing NIR emission property into chiral imprinted photonic (CIP) films. By employing a solvent immersion method, we successfully integrated Yb-PeNCs into these CIP films, thereby creating an optically unclonable surface. The resulting NIR-CPL emission adds a layer of advanced security to the optical PUF systems. These findings underscore the potential of solution-processable chiral films to play a pivotal role in advancing the next generation of PUFs.

Flexible, Photonic Films of Surfactant‐Functionalized Cellulose Nanocrystals for Pressure and Humidity Sensing

Most paints contain pigments that absorb light and fade over time. A robust alternative can be found in nature, where structural coloration arises from the interference of light with submicron features. Plant‐derived, cellulose nanocrystals (CNCs) mimic these features by self‐assembling into a cholesteric liquid crystal that exhibits structural coloration when dried. While much research has been done on CNCs in aqueous solutions, less is known about transferring CNCs to apolar solvents that are widely employed in paints. This study uses a common surfactant in agricultural and industrial products to suspend CNCs in toluene . Surprisingly, a stable liquid crystal phase is formed within hours, even with concentrations of up to 50 wt%. Evaporating the apolar CNC suspensions results in photonic films with peak wavelengths ranging from 660 to 920 nm. The resulting flexible films have variable mechanical properties with surfactant content, allowing for an optical response with applied force. The films also act as humidity sensors, with increasing relative humidity swelling the films, yielding a redshift in the reflected wavelength. With the addition of a single surfactant, CNCs can be made compatible with existing production methods of industrial coatings, while improving the strength and responsiveness of structurally colored films to external stimuli.

Deep-eutectic-solvent modulation of self-assembled multi-responsive films based on polyvinyl alcohol/cellulose nanocrystal and grape skin red for highly sensitive food monitoring

To enhance the mechanics performance, sensitivity and response range of multi-responsive photonic films, herein, a facile method for fabricating multi-responsive films is demonstrated using the evaporative self-assembly of a mixture of grape skin red (GSR), cellulose nanocrystal (CNC), polyvinyl alcohol (PVA) and deep eutectic solvent (DES). The prepared materials exhibited excellent thermal stability, strain properties, solvent resistance, ultraviolet (UV) resistance and antioxidant activity. Compared to a pure PVA film, the presence of GSR strengthened the antioxidant property of the film by 240.1 % and provided excellent UV barrier capability. The additional cross-linking of DES and CNC promoted more efficient phase fusion, yielding a film strain of 41.5 %. The addition of hydrophilic compound GSR, wetting and swelling due to the DES and the surface inhomogeneity of the films rendered the multi-responsive films high sensitivity, wide response range and multi-cyclic stability in environments with varying pH and humidity. A sample application showed that a PVA/CNC/DES film has the potential to differentiate between fresh, sub-fresh and fully spoiled shrimps. The above results help in designing intelligent thin film materials that integrate antioxidant properties, which help in monitoring the changes in food freshness and food packaging.

Responsive cellulose nanocrystal / acrylamide / poly (ethylene glycol) photonic films with chiral nematic structures by co-assembly and photopolymerization

Cellulose nanocrystals (CNCs), acrylamide (AAm) and poly (ethylene glycol) (PEG) can be co-assembled and photopolymerized into responsive, patterned photonic films with chiral nematic (N*) structures. Here, we report stimuli-responsive CNC/AAm/ PEG composite films (CFs) for use in humidity sensing. With the increase of AAm content, the CFs had an increased helical pitch and showed a red shift. With the adding of PEG, the CFs can quickly capture or release water molecules in air, which resulted in the changes of the helical pitch in N* structures and the structural color. After photopolymerization, the elastic modulus, hardness by nanomechanical testing and tensile strength of polymer films (PFs) were improved compared with CFs. The elastic modulus and hardness of PFs increased with the increase of AAm content. PFs and CFs showed different swelling properties in solutions with different EtOH / H2O ratio. Due to the swelling properties difference between CFs and PFs, partial photopolymerized photonic film showed photonic pattern. This research provides a new method to prepare photonic films with sensitive color response to humidity and photonic pattern, which has potential applications in the fields of sensing, anti-counterfeiting, and decoration.

Slow Photonic Effect Inducing Improved H2 Generation in Photonic Films with Chiral Nematic Structure

AbstractIntegrating photonic crystals (PCs) into the design of a photocatalyst can significantly enhance its light‐harvesting capability. PCs can manipulate the propagation of light uniquely within a material and reduce its group velocity, thereby enhancing the absorption factor for photocatalysts. However, the slow photon effect in photoactive films with chiral nematic structures has not been reported yet, especially at the blue edge of the photonic bandgap. This work proposes a straightforward one‐pot method to fabricate various photonic films with chiral nematic, namely g‐C3N4/SiO2, TiO2/SiO2, and g‐C3N4/TiO2/SiO2. The sol‐gel biotemplating formulation using cellulose nanocrystals successfully leads to the elaboration of films exhibiting variable iridescent colors with photonic bandgap from UV to visible range. The tunable wavelength of the Bragg peak reflection offers the opportunity to access a region with a slow photonic effect, which directly impacts the light‐harvesting properties of the photoactive material. It is demonstrated that the H2 generation is significantly enhanced when the blue edge of the photonic bandgap position overlapped with the absorbance band of the photocatalyst. These results offer the opportunity to design photonic materials with chiral nematic structure and optimize the photocatalytic performance for energy application.

Bioinspired Polymer Films with Surface Ordered Pyramid Arrays and 3D Hierarchical Pores for Enhanced Passive Radiative Cooling.

Passive radiative cooling (PRC) has been acknowledged to be an environmentally friendly cooling technique, and especially artificial photonic materials with manipulating light-matter interaction ability are more favorable for PRC. However, scalable production of radiative cooling materials with advanced biologically inspired structures, fascinating properties, and high throughput is still challenging. Herein, we reported a bioinspired design combining surface ordered pyramid arrays and internal three-dimensional hierarchical pores for highly efficient PRC based on mimicking natural photonic structures of the white beetle Cyphochilus' wings. The biological photonic film consisting of surface ordered pyramid arrays with a bottom side length of 4 μm together with amounts of internal nano- and micropores was fabricated by using scalable phase separation and a quick hot-pressing process. Optimization of pore structures and surface-enhanced photonic arrays enables the bioinspired film to possess an average solar reflectance of ∼98% and a high infrared emissivity of ∼96%. A temperature drop of ∼8.8 °C below the ambient temperature is recorded in the daytime. Besides the notable PRC capability, the bioinspired film exhibits excellent flexibility, strong mechanical strength, and hydrophobicity; therefore, it can be applied in many complex outdoor scenarios. This work provides a highly efficient and mold replication-like route to develop highly efficient passive cooling devices.

Harnessing the synergy of ZrO2 and SiO2 dielectric micro-/nanoparticles in polymer-based photonic films for robust passive daytime radiative cooling

Polymer-based materials emerge as promising building blocks for passive daytime radiative cooling (PDRC) due to their affordability and ease of production. Enhancing these polymers with inorganic particle doping has shown to boost their mechanical properties and light scattering ability, a result of the increased refractive index contrast with air. However, the incorporation of a single type of inorganic particle often falls short in optimizing overall performance. Herein, we introduce a novel approach by simultaneously integrating high refractive index zirconium dioxide (ZrO2) and wide band gap silicon dioxide (SiO2) dielectric particles into polydimethylsiloxane (PDMS) matrix. This dual-particle strategy synergistically improves the radiative cooling capabilities of the resulting photonic film. Remarkably, with a thickness of 1,000 μm, it achieves an impressive 96.7% reflection of solar irradiance, while maintaining a high emissivity of 95.2% in the atmospheric window. Under solar intensity of ∼836.7 W/m2, it delivers an average cooling power of 82.42 W/m2, achieving a substantial sub-ambient temperature drop of up to 8.26 °C. We further explored its effectiveness in enhancing freshwater collection efficiency, leveraging its radiative cooling properties. Furthermore, the photonic film also exhibits versatile properties including flexibility, hydrophobicity, thermal stability, color scalability, and weather resistance, thus enhancing its suitability for various practical applications.

Flexible multiple-stimulus-responsive photonic films based on layer-by-layer assembly of cellulose nanocrystals and deep eutectic solvents

Photonic crystal materials responding to environmental stimuli are important in sensors, intelligent detection, and anti-counterfeiting. However, traditional photonic materials usually lack tunable color and sufficient color suppleness, hindering their practical applications. Here, we report a facile strategy to achieve mechanical and color-tunable photonic films by doping deep eutectic solvents (DES) into cellulose nanocrystals (CNC) using layer-by-layer assembly. The amount of DES and several assembly layers were vital in determining the structure color and mechanical and response properties in the CNC photonic films. The experimental results revealed that DES could endow CNC suspension systems with high zeta potential, high viscoelasticity, and low transmittance. The tiny DES compensated for the insufficient flexibility of the CNC film, resulting in a wide color range, high solvent discrimination ability, and multi-color at several view angles. Moreover, photonic crystal film also played an important role in intelligent display and could be applied to traffic reflective signs to remind pedestrians and drivers of road safety and as smart labels for indoor humidity detection. These characteristics of the CNC photonic films could provide a promising strategy for developing advanced intelligent sensors, detection, and anti-counterfeiting materials.

Symmetric and Asymmetric Fabry–Pérot Cavity Design for a Dual-Mode Thermal Management Photonic Film with High-Purity Color

Symmetric and Asymmetric Fabry–Pérot Cavity Design for a Dual-Mode Thermal Management Photonic Film with High-Purity Color