Colloidal crystals develop structural colors through wavelength-selective diffraction. Recently, a granular format of colloidal crystals has emerged as building blocks to construct macroscopic photonic surfaces or architectures with high reconfigurability through the secondary assembly. Here, we design elastic photonic microcapsules containing colloidal crystallites along the inner wall as a building block. Water-in-oil-in-water double-emulsion templates are microfluidically prepared to have an aqueous dispersion of polystyrene particles in the inner droplet and polydimethylsiloxane prepolymers in the shell. Colloidal particles are enriched in the presence of depletant and salt by osmotic compression, with the crystallization at the inner interface by depletion attraction. The number of nucleation sites depends on the rate of the enrichment, which enables control over the size and surface coverage of the crystallites with osmotic conditions. The enrichment is ceased by transferring the droplets into an isotonic solution, and the oil shell is cured to form an elastic membrane. As the elastic microcapsules have a large void in the core, they are deformable without structural damage in the crystallites. Therefore, the microcapsules can be closely packed to form macroscopic surfaces while achieving a high quality of structural colors with a collection of crystallites aligned along the flattened membrane.

Photonic materials with a periodic change of refractive index show unique optical properties through wavelength-selective diffraction and modulation of optical density of state, which is promising for various optical applications....

Colloidal crystals have been tailored in a format of microspheres to use them as a building block to construct macroscopic photonic surfaces. However, the polycrystalline grains grown from the spherical surface usually exhibit low reflectivity. Although single-crystalline microspheres have been produced, it is difficult to control the crystal orientation. Here, we design spherical microcapsules with density anisotropy that contain single-crystalline grains along the heavy side. The microcapsules spontaneously align to have a heavy side down under the action of gravity and display a bright and uniform reflection color from the entire surface of the grains. Key to the success is the use of gentle centrifugal force to initiate nucleation and grow single-crystalline grains from the heavy side through depletion attraction. The microcapsules have density anisotropy due to the heterogeneity of the shell thickness, which causes them to self-align under centrifugation. At the same time, particles are accumulated on the heavy side, which produces many tiny grains on the heavy side immediately after the centrifugation. With controlled depletion attraction among particles, only a few grains survive during postincubation through Ostwald ripening, and one or a few giant single-crystalline grains are finally produced along the heavy side of each microcapsule.

Colloidal crystals are designed as photonic microparticles for various applications. However, conventional microparticles generally have only one stopband from a single lattice constant, which restricts the range of colors and optical codes available. Here, photonic microcapsules are created that contain two or three distinct crystalline grains, resulting in dual or triple stopbands that offer a wider range of colors through structural color mixing. To produce distinct colloidal crystallites from binary or ternary colloidal mixtures, the interparticle interaction is manipulated using depletion forces in double‐emulsion droplets. Aqueous dispersions of binary or ternary colloidal mixtures in the innermost droplet are gently concentrated in the presence of a depletant and salt by imposing hypertonic conditions. Different‐sized particles crystallize into their own crystals rather than forming random glassy alloys to minimize free energy. The average size of the crystalline grains can be adjusted with osmotic pressure, and the relative ratio of distinct grains can be controlled with the mixing ratio of particles. The resulting microcapsules with small grains and high surface coverage are almost optically isotropic and exhibit highly‐saturated mixed structural colors and multiple reflectance peaks. The mixed color and reflectance spectrum are controllable with the selection of particle sizes and mixing ratios.