Disordered Inverse Photonic Beads Assembled From Linear Block Copolymers

Abstract

Abstract Structurally colored colloids, or photonic pigments, offer a sustainable alternative to conventional dyes, yet existing systems are constrained by limited morphologies and complex synthesis. In particular, achieving angle‐independent color typically relies on disordered inverse architectures formed from synthetically demanding bottlebrush block copolymers (BCPs), hindering scalability and functional diversity. Here, we report a conceptually distinct strategy to assemble three‐dimensional inverse photonic glass microparticles using amphiphilic linear BCPs (poly(styrene‐ block ‐4‐vinylpyridine), PS‐ b ‐P4VP) via an emulsion‐templated process. By employing trans‐1,2‐dichloroethylene to promote interfacial water infiltration, nanoscale aqueous domains form within the organic phase and direct short‐range‐ordered pore structures. Evaporative solidification arrests these structures into porous photonic beads with angle‐independent color. Systematic control of surfactant alkyl chain length and BCP molecular weight enables precise tuning of pore size, shell thickness, and visible‐range optical output. Furthermore, post‐chemical modification via quaternization of P4VP provides an orthogonal chemical handle to modulate interfacial instability and photonic behavior. This work expands the self‐assembly capabilities of linear BCPs and establishes a modular, scalable platform for producing structurally and chemically programmable photonic pigments.