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Colloidal particles with a repulsive interparticle potential spontaneously form crystalline lattices, which are used as a motif for photonic materials. It is difficult to predict the crystal arrangement in spherical volume as lattices are incompatible with a spherical surface. Here, the optimum arrangement of charged colloids is experimentally investigated by encapsulating them in double-emulsion drops. Under conditions of strong interparticle repulsion, the colloidal crystal rapidly grows from the surface toward the center of the microcapsule, forming an onion-like arrangement. By contrast, for weak repulsion, crystallites slowly grow and fuse through rearrangement to form a single-crystal phase. Single-crystal structure is energetically favorable even for strong repulsion. Nevertheless, a high energy barrier to colloidal rearrangement kinetically arrests the onion-like structure formed by heterogeneous nucleation. Unlike the isotropic onion-shaped product, the anisotropic single-crystal-containing microcapsules selectively display-at certain orientations but not others-one of the distinct colors from the various crystal planes.

Colloidal crystallization is analogous to the crystallization in bulk atomic systems in various aspects, which has been explored as a model system. However, a real-time probing of the phenomenon still remains challenging. Here, a levitation system for a study of colloidal crystallization is demonstrated. Colloidal particles in a levitated droplet are gradually concentrated by isotropic evaporation of water from the surface of the droplet, resulting in crystallization. The structural change of the colloidal array during crystallization is investigated by simultaneously measuring the volume and reflectance spectra of the droplet. The crystal nucleates from the surface of the droplet at which the volume fraction exceeds the threshold and then the growth proceeds. The crystal growth behavior depends on the initial concentrations of colloidal particles and salts which determine the overall direction of crystal growth and interparticle spacing, respectively. The results show that a levitating bulk droplet has a great potential as a tool for in situ investigation of colloidal crystallization.

Technologies to monitor microenvironmental conditions and its spatial distribution are in high demand, yet remain unmet need. Herein, photonic microsensors are designed in a capsule format that can be injected, suspended, and implanted in any target volume. Colorimetric sensors are loaded in the core of microcapsules by assembling core-shell colloids into crystallites through the depletion attraction. The shells of the colloids are made of a temperature-responsive hydrogel, which enables the crystallites to rapidly and widely tune the structural color in response to a change in temperature while maintaining close-packed arrays. The spherical symmetry of the microcapsules renders them optically isotropic, i.e., displaying orientation-independent color. In addition, as a solid membrane is used to protect the delicate crystallites from external stresses, their high stability is assured. More importantly, each microcapsule reports the temperature of its microenvironment so that a suspension of capsules can provide information on the spatial distribution of the temperature.

Chameleons use a non-close-packed array of guanine nanocrystals in iridophores to develop and tune skin colors in the full visible range. Inspired by the biological process uncovered in panther chameleons, we designed photonic films containing a non-close-packed face-centered-cubic array of silica particles embedded in an elastomer. The non-close-packed array is formed by interparticle repulsion exerted by solvation layers on the particle surface, which is rapidly captured in the elastomer by photocuring of the dispersion medium. The artificial skin exhibits a structural color that shifts from red to blue under stretching or compression. The separation between inelastic particles enables tuning without experiencing significant rearrangement of particles, providing elastic deformation and reversible color change, as chameleons do. The simple fabrication procedure consists of film casting and UV irradiation, potentially enabling the continuous high-throughput production. The mechanochromic property of the photonic films enables the visualization of deformation or stress with colors, which is potentially beneficial for various applications, including mechanical sensors, sound-vision transformers, and color display.

Recent advances in microfluidics have enabled the controlled production of multiple-emulsion drops with onion-like topology. The multiple-emulsion drops possess an intrinsic core-shell geometry, which makes them useful as templates to create microcapsules with a solid membrane. High flexibility in the selection of materials and hierarchical order, achieved by microfluidic technologies, has provided versatility in the membrane properties and microcapsule functions. The microcapsules are now designed not just for storage and release of encapsulants but for sensing microenvironments, developing structural colours, and many other uses. This article reviews the current state of the art in the microfluidic-based production of multiple-emulsion drops and functional microcapsules. The three main sections of this paper discuss distinct microfluidic techniques developed for the generation of multiple emulsions, four representative methods used for solid membrane formation, and various applications of functional microcapsules. Finally, we outline the current limitations and future perspectives of microfluidics and microcapsules.