Spider Silk Inspired Shape Adaptive and Heat Conductive Thermal Interface Materials

ABSTRACT Efficient dissipation of waste heat in chips with thermal interface materials (TIM) is essential for high‐performance electric devices. The superiorities of thermal conductance, dielectric insulation, and self‐healing capability make polymer composites promising candidates for TIM. However, the inherent rigidity limits its shape adaptive contact with chips/sinks. Inspired by the dimension‐crossover architecture of semi‐crystalline spider silk, we develop an electrically responsive semicrystalline ferroelectric polymer at elevated temperature. The crystalline domains stabilized by weak bonding networks create mechanical anchor points. It enables controllable loading and maintains efficient thermal pathways, depicting remarkable shape adaption (41% elongation) and directional thermal conductance (2.50 W·m −1 ⋅K −1 ). The dipole polarization induced localized crystallization, evolving from random coil to twisted to trans conformation in amorphous domains, imitates a controlled inter‐chain alignment in spider silk. Additionally, electric stimuli at 500 K activates a self‐healing process via reversible chain realignment, which extends the remaining lifetime of electronic devices. This electrically responsive TIM represents a significant advance in the design and optimization of next‐generation TIM, and offers a highlight insight into the process–structure–property relationship.