Materials in nature are characterized by structural order over multiple length scales have evolved for maximum performance and multifunctionality, and are often produced by self-assembly processes. A striking example of this design principle is structural coloration, where interference, diffraction, and absorption effects result in vivid colors. Mimicking this emergence of complex effects from simple building blocks is a key challenge for manmade materials. Here, we show that a simple confined selfassembly process leads to a complex hierarchical geometry that displays a variety of optical effects. Colloidal crystallization in an emulsion droplet creates micron-sized superstructures, termed photonic balls. The curvature imposed by the emulsion droplet leads to frustrated crystallization. We observe spherical colloidal crystals with ordered, crystalline layers and a disordered core. This geometry produces multiple optical effects. The ordered layers give rise to structural color from Bragg diffraction with limited angular dependence and unusual transmission due to the curved nature of the individual crystals. The disordered core contributes nonresonant scattering that induces a macroscopically whitish appearance, which we mitigate by incorporating absorbing gold nanoparticles that suppress scattering and macroscopically purify the color. With increasing size of the constituent colloidal particles, grating diffraction effects dominate, which result from order along the crystal's curved surface and induce a vivid polychromatic appearance. The control of multiple optical effects induced by the hierarchical morphology in photonic balls paves the way to use them as building blocks for complex optical assemblies-potentially as more efficient mimics of structural color as it occurs in nature.self-assembly | colloids | photonic crystal | structural color | hierarchy H ierarchical design principles, i.e., the structuration of material over multiple length scales, are ubiquitously used in nature to maximize functionality from a limited choice of available components. Hierarchically structured materials often provide better performance than their unstructured counterparts and novel properties can arise solely from the multiscale structural arrangement. Examples can be found in the extreme water repellency of the lotus leaf (1); the outstanding mechanical stability and toughness of sea creatures such as sea sponges (2) and abalone shells (3); and the bright coloration found in beetles, birds, and butterflies (4, 5).To achieve the strongest visual effects, many organisms combine optical effects arising from light interacting with structured matter at different length scales (6). Structural periodicity on the scale of visible light wavelengths can result in regular optical density variations that give rise to bright, iridescent colors due to pronounced interference effects (4). At the micron scale, regular structural features act as diffraction gratings that produce vivid, rainbow coloration (7) and are used to control scatteri...

Much of modern technology--from data encryption to environmental sensors to templates for device fabrication--relies on encoding complex chemical information in a single material platform. Here we develop a technique for patterning multiple chemical functionalities throughout the inner surfaces of three-dimensional (3D) porous structures. Using a highly ordered 3D photonic crystal as a regionally functionalized porous carrier, we generate complex wettability patterns. Immersion of the sample in a particular fluid induces its localized infiltration and disappearance of the bright color in a unique spatial pattern dictated by the surface chemistry. We use this platform to illustrate multilevel message encryption, with selective decoding by specific solvents. Due to the highly symmetric geometry of inverse opal photonic crystals used as carriers, a remarkable selectivity of wetting is observed over a very broad range of fluids' surface tensions. These properties, combined with the easily detectable optical response, suggest that such a system could also find use as a colorimetric indicator for liquids based on wettability.

Colorimetric litmus tests such as pH paper have enjoyed wide commercial success due to their inexpensive production and exceptional ease of use. Expansion of colorimetry to new sensing paradigms is challenging because macroscopic color changes are seldom coupled to arbitrary differences in the physical/chemical properties of a system. Here we present in detail the design of a "Wetting In Color Kit" (WICK), an inexpensive and highly selective colorimetric indicator for organic liquids that exploits chemically encoded inverse-opal photonic crystals to project minute differences in liquids' wettability to macroscopically distinct, easy-to-visualize structural color patterns. We show experimentally and corroborate with theoretical modeling using percolation theory that the highly symmetric structure of our large-area, defect-free SiO(2) inverse-opal films leads to sharply defined threshold wettability for liquid infiltration, occurring at intrinsic contact angles near 20° with an estimated resolution smaller than 5°. The regular structure also produces a bright iridescent color, which disappears when infiltrated with liquid, naturally coupling the optical and fluidic responses. To deterministically design a WICK that differentiates a broad range of liquids, we introduced a nondestructive quality control procedure to regulate the pore structure and developed two new surface modification protocols, both requiring only silanization and selective oxidation. The resulting tunable, built-in horizontal and vertical chemistry gradients let us tailor the wettability threshold to specific liquids across a continuous range. With patterned oxidation as a final step, we control the shape of the liquid-specific patterns displayed, making WICK easier to read. Using these techniques, we demonstrate the applicability of WICKs in several exemplary systems that colorimetrically distinguish (i) ethanol-water mixtures varying by only 2.5% in concentration; (ii) methanol, ethanol, and isopropyl alcohol; (iii) hexane, heptane, octane, nonane, and decane; and (iv) samples of gasoline (regular unleaded) and diesel. As wetting is a generic fluidic phenomenon, we envision that WICK could be suitable for applications in authentication or identification of unknown liquids across a broad range of industries.

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