Polymer Opals Research Articles

Extending Polymer Opal Structural Color Properties into the Near-Infrared

We report the fabrication and characterisation of near-IR reflecting films and coatings based on shear-assembled crystalline ensembles of polymer composite microspheres, also known as “polymer opals”. Extension of the emulsion polymerisation techniques for synthesis of tractable larger core-interlayer-shell (CIS) particles, of up to half a micron diameter, facilitates the engineering and processing of thin-film synthetic opals, with a tunable photonic stopband spanning an extended spectral range of λ ≈ 700–1600 nm. Samples exhibit strong “scattering cone” interactions, with considerable angular dependence and angle tuning possible, as measured with a goniometric technique. These intense optical resonances in the near-IR, particularly within the important region around λ ~ 800 nm, combined with an appreciable translucency within the visible light spectrum, is indicative of the potential applications in coatings technologies and solar cells.

Dial-In Synthesis of 'Polymer Opal' Core-Interlayer-Shell Composite Nanoparticles.

The emulsion polymerization process via which core-interlayer-shell polymer nanoparticles are synthesized is engineered to offer a crucial control of the eventual size and monodispersity of the polystyrene (PS) cores. We examine the role of key experimental parameters, optimizing the temperature, reactant purity, and agitation (stirring) rate. The subsequent addition of a poly(methyl-methacrylate) (PMMA) grafting layer and a poly(ethyl-acrylate) (PEA) shell layer produces composite particles, which are shear-orderable into opaline films, known as 'polymer opals'. We thus demonstrate pathways toward a 'dial-in' process, where the time taken to obtain the target core size is mapped to the expected resultant structural color. At reaction temperatures of 60 and 70 °C, viable conditions are found where all syntheses give an excellent level of monodispersity (polydispersity index < 0.02), suitable for interlayer and shell growth. These reports may be readily applied to a wider industrial scale fabrication pipeline for these polymeric photonic materials.

Spectroscopic Ellipsometry and Optical Modelling of Structurally Colored Opaline Thin-Films

The method of spectroscopic ellipsometry is applied to complex periodic nanomaterials, consisting of shear-ordered polymeric nanosphere composites, with intense resonant structural color. A corresponding multilayer optical quasi-model of the system, parametrizing the inherent degree of sample disorder and encompassing key properties of effective refractive-index and index-contrast, is developed to elucidate the correlation between the ∆ and Ψ ellipsometric parameters and the shear-induced opaline crystallinity. These approaches offer reliable means of in-line tracking of the sample quality of such “polymer opals” in large scale processing and applications.

Embedding Photoacids into Polymer Opal Structures: Synergistic Effects on Optical and Stimuli-Responsive Features.

Opal films with their vivid structural colors represent a field of tremendous interest and obtained materials offer the possibility for many applications, such as optical sensors or anti-counterfeiting materials. A convenient method for the generation of opal structures relies on the tailored design of core-interlayer-shell (CIS) particles. Within the present study, elastomeric opal films were combined with stimuli-responsive photoacids to further influence the optical properties of structurally colored materials. Starting from cross-linked polystyrene (PS) core particles featuring a hydroxy-rich and polar soft shell, opal films were prepared by application of the melt-shear organization technique. The photoacid tris(2,2,2-trifluoroethyl) 8-hydroxypyrene-1,3,6-trisulfonate (TFEHTS) could be conveniently incorporated during freeze-drying the particle dispersion and prior to the melt-shear organization. Furthermore, the polar opal matrix featuring hydroxylic moieties enabled excited-state proton transfer (ESPT), which is proved by spectroscopic evaluation. Finally, the influence of the photoacid on the optical properties of the 3-dimensional colloidal crystals were investigated within different experimental conditions. The angle dependence of the emission spectra unambiguously shows the selective suppression of the photoacid’s fluorescence in its deprotonated state.

Mechanochromic Sensors: Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals (Adv. Funct. Mater. 31/2020)

Mechanochromic Sensors: Mechanochromic and Thermochromic Sensors Based on Graphene Infused Polymer Opals (Adv. Funct. Mater. 31/2020)

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.

Highly monodisperse zwitterion functionalized non-spherical polymer particles with tunable iridescence.

A facile and simple synthetic route towards functionalized non-spherical polymer particles (NSP) with tunable morphologies and iridescence is presented. Monodisperse particles with unique zwitterionic functionality were synthesized via emulsifier-free emulsion polymerization in a single step process. The sulfobetaine comonomer was utilized to induce phase separation in the course of polymerization to achieve anisotropic NSP with controlled morphologies such as quasi-spherical with protruding structures like bulge, eye-ball, and snowman-like nanostructures. Both SEM and TEM analyses revealed anisotropic particles, and phase-separated protrusion morphology with a small increase in aspect ratio. By taking advantage of the monodisperse, colloidally stable NSPs, template free photonic crystal arrays were fabricated through a bottom-up approach. The particles readily self-assemble and exhibit a photonic bandgap with vivid structural colors that arise from ordered structures of different morphologies. Additionally, the salt-responsive photonic crystals also possess tunable color-changing characteristics.

Tuning of Structural Colors Like a Chameleon Enabled by Shape-Memory Polymers.

Nature often uses structuring of materials for coloration rather than incorporating dye molecules, since single-construction materials are capable of producing any vivid visible color in plants and insects. By precisely engineering features that diffract or scatter light, more recently, humans have created similarly intense non-fading colors. Stretchable polymer opals have emerged as a single material which can dynamically shift across the whole visible spectrum using structural colors, by temporary stretching or compression. For energy efficiency and practical considerations, however, it is necessary to fix semi-permanently desired colors without continuous stretching or application of other stimuli or energy. Here, a polymer opal incorporating a shape-memory polymer embedded in its matrix can keep a particular color fixed without the application of external forces, yet can be reprogrammed to a different fixed color on demand. The influence of the material composition on its optical appearance, shape-fixity, and shape recovery abilities in controlled stretch experiments is quantified. High-speed printing-compatible localized compression pattern imprinting is shown to generate stable but easily erasable color patterns. This opens up the potential for durable and energy-efficient yet reusable and reconfigurable displays, wearables, or packaging and security labeling based on such polymeric film materials.

Strong Photonic-Band-Gap Effect on the Spontaneous Emission in 3D Lead Halide Perovskite Photonic Crystals.

Stimulated emission in perovskite-embedded polymer opal structures is investigated. A polymer opal structure is filled with a perovskite, and perovskite photonic crystals are prepared. The spontaneous emission of the perovskite embedded in the polymer opal structures exhibits clear signatures of amplified spontaneous emission (ASE) via gain modulation. The difference in refractive-index contrast between the perovskite and the polymer opal is large enough for retaining photonic-crystals properties. The photonic band gap has a strong effect on the fluorescence emission intensity and lifetime. The stimulated emission spectrum exhibits a narrow ASE rather than a wide fluorescence peak in the thin film.

Organic–inorganic hybrid optical foils with strong visible reflection, excellent near infrared-shielding ability and high transparency

Research on functional flexible films has recently been attracting widespread attention especially with regards to foils, which can be designed artificially on the basis of the practical requirements. In this work, a foil with high visible reflection and a strong near infrared shielding efficiency was prepared by a simple wet chemical method. In the process of making this kind of optical foil, emulsion polymerization was first introduced to synthesize polymer opals, which were further compressed between two pieces of polyethylene terephthalate (PET) foil under polymer melting temperature to obtain a photonic crystal film with a strong reflection in the visible region to block blue rays. The following step was to coat a layer of the inorganic nano paint, which was synthesized by dispersing Cs-doped WO3 (CWO) nanoparticles homogenously into organic resin on the surface of the PET to achieve a high near infrared shielding ability. The final composite foil exhibited unique optical properties such as high visible reflectance (23.9%) to block blue rays, and excellent near infrared shielding efficiency (98.0%), meanwhile it still maintained a high transparency meaning that this foil could potentially be applied in energy-saving window films. To sum up, this study provides new insight into devising flexible hybrid films with novel optical properties, which could be further extended to prepare other optical films for potential use in automobile, architectural and other decorative fields.

Functional Polymer Opals and Porous Materials by Shear-Induced Assembly of Tailor-Made Particles.

Photonic band-gap materials attract enormous attention as potential candidates for a steadily increasing variety of applications. Based on the preparation of easily scalable monodisperse colloids, such optically attractive photonic materials can be prepared by an inexpensive and convenient bottom-up process. Artificial polymer opals can be prepared by shear-induced assembly of core/shell particles, yielding reversibly stretch-tunable materials with intriguing structural colors. This feature article highlights recent developments of core/shell particle design and shear-induced opal formation with focus on the combination of hard and soft materials as well as crosslinking strategies. Structure formation of opal materials relies on both the tailored core/shell architecture and the parameters for polymer processing. The emphasis of this feature article is on elucidating the particle design and incorporation of addressable moieties, i.e., stimuli-responsive polymers as well as elaborated crosslinking strategies for the preparation of smart (inverse) opal films, inorganic/organic opals, and ceramic precursors by shear-induced ordering.

Generating Bulk-Scale Ordered Optical Materials Using Shear-Assembly in Viscoelastic Media

We review recent advances in the generation of photonics materials over large areas and volumes, using the paradigm of shear-induced ordering of composite polymer nanoparticles. The hard-core/soft-shell design of these particles produces quasi-solid “gum-like” media, with a viscoelastic ensemble response to applied shear, in marked contrast to the behavior seen in colloidal and granular systems. Applying an oscillatory shearing method to sub-micron spherical nanoparticles gives elastomeric photonic crystals (or “polymer opals”) with intense tunable structural color. The further engineering of this shear-ordering using a controllable “roll-to-roll” process known as Bending Induced Oscillatory Shear (BIOS), together with the interchangeable nature of the base composite particles, opens potentially transformative possibilities for mass manufacture of nano-ordered materials, including advances in optical materials, photonics, and metamaterials/plasmonics.

Iridescent structural colors from self-assembled polymer opal of polythiourethane microspheres

Artificial structural color materials from self-assembled colloidal spheres, which are similar to natural opals, are currently a subject of extensive investigation. However, the shortage of available colloidal spheres, especially polymer spheres for building artificial opals is still a major restriction for their practical application. Herein, a new kind of artificial opals with iridescent structural colors were prepared from the self-assembly of novel polythiourethane microspheres (PTUMS). The PTUMS with narrow size distribution were prepared through a simple phase separation process. Particle sizes can be easily adjusted from 175 nm to 304 nm, which is important for the construction of tunable structural colors. Sufficient surface charges were obtained from the reaction between the terminal isocyanate groups and water. Thus, PTUMS can arranged into periodic opal structures through self-assembly process and generate iridescent structural colors. The present study provided an effective and convenient approach to prepare artificial structural color materials from new kind of polymer microspheres. This was very important for the practical application of artificial opals in coating and paints.

Nanoassembly of Polydisperse Photonic Crystals Based on Binary and Ternary Polymer Opal Alloys

Ordered binary and ternary photonic crystals, composed of different sized polymer-composite spheres with diameter ratios up to 120%, are generated using bending induced oscillatory shearing (BIOS). This viscoelastic system creates polydisperse equilibrium structures, producing mixed opaline colored films with greatly reduced requirements for particle monodispersity, and very different sphere size ratios, compared to other methods of nano-assembly.

Large-scale ordering of nanoparticles using viscoelastic shear processing.

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Fast Assembly of Gold Nanoparticles in Large-Area 2D Nanogrids Using a One-Step, Near-Infrared Radiation-Assisted Evaporation Process.

When fabricating photonic crystals from suspensions in volatile liquids using the horizontal deposition method, the conventional approach is to evaporate slowly to increase the time for particles to settle in an ordered, periodic close-packed structure. Here, we show that the greatest ordering of 10 nm aqueous gold nanoparticles (AuNPs) in a template of larger spherical polymer particles (mean diameter of 338 nm) is achieved with very fast water evaporation rates obtained with near-infrared radiative heating. Fabrication of arrays over areas of a few cm(2) takes only 7 min. The assembly process requires that the evaporation rate is fast relative to the particles' Brownian diffusion. Then a two-dimensional colloidal crystal forms at the falling surface, which acts as a sieve through which the AuNPs pass, according to our Langevin dynamics computer simulations. With sufficiently fast evaporation rates, we create a hybrid structure consisting of a two-dimensional AuNP nanoarray (or "nanogrid") on top of a three-dimensional polymer opal. The process is simple, fast, and one-step. The interplay between the optical response of the plasmonic Au nanoarray and the microstructuring of the photonic opal results in unusual optical spectra with two extinction peaks, which are analyzed via finite-difference time-domain method simulations. Comparison between experimental and modeling results reveals a strong interplay of plasmonic modes and collective photonic effects, including the formation of a high-order stopband and slow-light-enhanced plasmonic absorption. The structures, and hence their optical signatures, are tuned by adjusting the evaporation rate via the infrared power density.

Polymer opal with brilliant structural color under natural light and white environment

Abstract

Selectively Patterning Polymer Opal Films via Microimprint Lithography

Large-scale structural color flexible coatings have been hard to create, and patterning color on them is key to many applications, including large-area strain sensors, wall-size displays, security devices, and smart fabrics. To achieve controlled tuning, a micro-imprinting technique is applied here to pattern both the surface morphology and the structural color of the polymer opal films (POFs). These POFs are made of 3D ordered arrays of hard spherical particles embedded inside soft shells. The soft outer shells cause the POFs to deform upon imprinting with a pre-patterned stamp, driving a flow of the soft polymer and a rearrangement of the hard spheres within the films. As a result, a patterned surface morphology is generated within the POFs and the structural colors are selectively modified within different regions. These changes are dependent on the pressure, temperature, and duration of imprinting, as well as the feature sizes in the stamps. Moreover, the pattern geometry and structural colors can then be further tuned by stretching. Micropattern color generation upon imprinting depends on control of colloidal transport in a polymer matrix under shear flow and brings many potential properties including stretchability and tunability, as well as being of fundamental interest.

The rheology and processing of “edge sheared” colloidal polymer opals

This paper is concerned with the rheology and processing of solvent-free core shell “polymer opals” that consist of a soft outer shell grafted to hard colloidal polymer core particles. Strong iridescent colors can be produced by shearing the material in a certain way that causes the initially disordered spheres to rearrange into ordered crystalline structures and produce colors by diffraction and interference of multiple light scattering, similar to gemstone opals. The basic linear viscoelastic rheology of a polymer opal sample was determined as a function of temperature, and the material was found to be highly viscoelastic at all tested temperatures. A Cambridge multipass rheometer was specifically modified in order to make controlled mechanical measurements of initially disordered polymer opal tapes that were sandwiched between protective polyethylene terephthalate sheets. Axial extension, simple shear, and a novel “edge shearing” geometry were all evaluated, and multiple successive experiments of the edge shearing test were carried out at different temperatures. The optical development of colloidal ordering, measured as optical opalescence, was quantified by spectroscopy using visible backscattered light. The development of opalescence was found to be sensitive to the geometry of deformation and a number of process variables suggesting a complex interaction of parameters that caused the opalescence. In order to identify aspects of the deformation mechanism of the edge shearing experiment, a separate series of in situ optical experiments were carried out and this helped indicate the extent of simple shear generated with each edge shear deformation. The results show that strong ordering can be induced by successive edge shearing deformation. The results are relevant to polymer opal rheology, processing, and mechanisms relating to ordering within complex viscoelastic fluids.

Hydrophobic structural color films with bright color and tunable stop-bands

Hydrophobic structural color films have attracted a special attention due to the great advantages in application, which currently become a research hot-spot. This study presents a convenient approach to fabricate hydrophobic structural color films by modifying self-assembled polymer opal from cross-linked polystyrene microspheres and polydimethylsiloxane. The obtained films exhibited several unique characteristics, such as a high water contact angle of 137°, bright structural color, and tunable stop-bands. Additionally, the combination of hydrophobicity and tunable stop-bands was significant for potential application in paint and external decoration of architectures. The present result opens new vistas for the research of functional films, using thermal-assisted self-assembly as a simple method that is cheap and commonly available.