Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal assemblies

Significance Controlling the internal structure over multiple length scales can produce materials with superior properties. This hierarchical design is ubiquitous in nature where materials have evolved to show maximum functionality from a limited choice of available building blocks. Mimicking the emergence of functionality from simple building blocks is a key challenge for man-made materials. Here, we show how a simple confined self-assembly of colloidal particles leads to a complex geometry that displays a surprising variety of optical effects. These effects are a result of the intricate interaction of light with the structural features at different length scales, and the geometry of the self-assembled structure. The results underline the importance of controlling assembly processes over multiple length scales to tailor properties and maximize performance. 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 man-made materials. Here, we show that a simple confined self-assembly 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.