Customized 3D Hierarchical Patterning for Information Encryption

Abstract Hierarchical structures have shown broad application due to their unique properties arising from multiscale structural synergy. However, precise integration of micro/nanomaterials across multiple scales in three dimensions remains a significant challenge. Herein, a novel 3D hierarchical structures (3D‐HSs) patterning method is proposed based on print‐assisted plasmonic nanochemistry. By leveraging the dual confinement of the nucleation region and the localized near‐field, Ag nanoparticles are precisely grown on the 3D printed entity surface and organized into a ring‐like structure within the nanoholes. The resulting 3D‐HSs consist of macroscale printed entities, submicron‐scale Au nanohole arrays, and Ag nanoparticle assemblies, achieving hierarchical organization from macro‐ to nanoscale. Moreover, spatially resolved dual‐layer 3D architectures are constructed, achieving highly correlated patterns and the precise allocation of particle assemblies on the same plane. The synergistic interplay between hierarchical components leads to spatially resolved pattern information and region‐specific surface‐enhanced Raman scattering (SERS) performance, offering a multi‐level, high‐security anti‐counterfeiting strategy that integrates optical and molecular encoding. This strategy combines the programmability of additive manufacturing with the precision of nanochemistry processing, establishing a versatile platform for constructing hierarchically organized 3D structures with tunable functionality and spatial resolution.