Dry Bondable Porous Silk Fibroin Films for Embedding Micropatterned Electronics in Hierarchical Silk Nacre

Abstract Future structural materials is not only be lightweight, strong, and tough, but also capable of integrating functions like sensing, adaptation, self‐healing, deformation, and recovery as needed. Although bio‐inspired materials are well developed, directly integrating microelectronic patterns into nacre‐mimetic structures remains challenging, limiting the widespread application of electronic biomimetic materials. Here, an in situ freeze‐drying method is reported for the successful preparation of porous silk fibroin materials that can achieve dry bonding. The in situ freeze‐drying method preserves the structural integrity of the lyophilized membrane while reducing procedural steps, achieving control over pore gradient not feasible with traditional freeze‐drying techniques. By leveraging their smooth surfaces and capacity to support heat transfer patterns, layer‐by‐layer assembly at a macroscopic scale is achieved. The material's excellent mechanical properties, controllable graded structure, and adjustable degradation behavior enable the construction of electronically functionalized hierarchical structures. Additionally, the dry‐state, layer‐by‐layer bonding method for porous polymer films provides advantages in precision control, mechanical stability, functional versatility, hierarchical structuring, and scalability. It represents an innovative approach, offering multi‐functional and customizable bulk materials, especially suited for biomedical applications. This work offers an effective pathway for developing high‐performance and multifunctional biomimetic devices with controllable hierarchical structures.