Shape morphing materials have been extensively studied to control the formation of sophisticated three-dimensional (3D) structures and devices for a broad range of applications. Various methods, including the buckling of pre-strained bilayer composites, stimuli-responsive shape-shifting of shape memory polymers, and hydrogels, have been previously employed to transform 2D sheets to 3D structures and devices. However, the residual stress locked in these shape-shifting structures will drive them to gradually revert to their original layouts upon the removal of external stimuli or constrains. Here, we report a multistimuli-responsive vitrimer (m-vitrimer) bearing thermal- and photo-reversible disulfide bonds as shape programmable and healable materials for functional 3D devices. The mechanical properties and thermomechanical properties of vitrimer were tuned by altering the disulfide content and catalyst loading. Heat and light exposure induces effective stress relaxation and network rearrangement, enabling material shape programming and healing. We demonstrate that printed flexible smart electronics are fabricated using the m-vitrimer as a matrix and printed conductive silver nanoparticles as conductive wire. The printed electronics possess good electro-mechanical properties, strong interfacial bonding, and thermal- and photo-responsive shape programming. Moreover, the m-vitrimer can be healed upon damage by heat and light, which partially restores silver conductivity and protect the electronics from further damage. The converging of multi-stimuli-responsive polymers and printed electronics for functional 3D devices have the potential of finding broad applications in smart and morphing electronics, biomedical devices, and 4D printing.

形状变形材料已得到广泛研究，以控制复杂的三维（3D）结构和设备的形成，从而可用于广泛的应用。先前已经采用了各种方法，包括将预应变的双层复合材料屈曲，形状记忆聚合物的刺激响应形变和水凝胶，将2D薄片转换为3D结构和设备。但是，锁定在这些形变结构中的残余应力将驱使它们在消除外部刺激或约束后逐渐恢复其原始布局。在这里，我们报道了一种带有热和光可逆二硫键的多刺激响应微晶玻璃（m-vitrimer），它是功能性3D设备的形状可编程和可修复材料。通过改变二硫键含量和催化剂负载量来调整微晶硅的机械性能和热机械性能。暴露在热和光下可有效缓解应力和网络重排，从而实现材料形状的编程和修复。我们演示了使用m-vitrimer作为基质和印刷导电银纳米颗粒作为导线制造的印刷柔性智能电子产品。印刷电子产品具有良好的机电性能，牢固的界面结合以及热响应和光响应形状编程。此外，m-vitrimer可以在受热和光照损坏的情况下得到修复，从而部分恢复银的导电性并保护电子器件免受进一步损坏。