Photothermally Synergistic Cross‐Linking in Three‐Component Smart Materials for Precise and Tough Micro and Nanopatterning

Abstract Modulating the molecular design of polymers to create highly integrated flexible structures with superior mechanical properties and precise, on‐demand patterning has considerable potential for applications in mechanical, electronic, and biomedical fields. However, achieving an optimal balance of high‐strength, high‐toughness, and low‐defect patterning within micro and nanoscale dimensions remains challenging. This study investigates photothermally synergistic cross‐linked three‐component‐patterned materials (TCPMs) for the first time. These materials form a cross‐linked network through a photoinduced thiol–ene click reaction of polythiol–norbornene and a thermally initiated Diels–Alder (D–A) reaction of difuran‐maleimide, enabling controlled solubility switching and facilitating directional pattern transfer after development. On characterizing the mechanical behavior and pattern quality, TCPM achieves a pattern line width of 136 nm, a sensitivity of 25.4 mJ cm −2 , an elongation rate of 330%, and an elastic modulus of 1.44 GPa. In addition, by constructing a photothermal cross‐linking network and balancing the proportions of the soft and hard segments, the patterned TCPM can maintain high stability under external stimuli while exhibiting controllable mechanical adaptive behavior owing to its innovative molecular structure. Overall, this unique combination leads to new possibilities for the application of TCPM in fields such as flexible electronics, micro and nanosensing and biomedical engineering.