Three-Dimensional Printing Ultrastrong, Ultraductile Micro/nano Silicon Oxycarbide Ceramics Derived from a Monolithic Preceramic Resin

Polymer-derived ceramics (PDCs) are promising candidates for fabricating three-dimensional (3D) micro/nanodevices. However, their advancement has been constrained by a persistent challenge in that precursor simplicity, high-fidelity shaping of complex 3D architectures, and superior mechanical properties in the final ceramic are incompatible. To overcome this, an extremely simple photosensitive preceramic resin comprising only polycarbosilane and a photoinitiator is proposed to fabricate high-precision 3D PDC microstructures with intricate geometries and exceptional mechanical performance. A process involving prebaking and two-photon polymerization forms stable 3D preceramic polymer networks, which after pyrolysis yield defect-free amorphous SiOC ceramics exhibiting high shape fidelity and low linear shrinkage (28% at 1000 °C). The ceramics show temperature-dependent mechanical properties, with micropillar compressive strength reaching 6.41 GPa (1000 °C) and 7.55 GPa (1200 °C). Leveraging these properties, lightweight high-strength mechanical metamaterials with 20% relative density are fabricated, achieving a compressive strength of 0.54 GPa and a failure strain exceeding 10%. Functional microneedle arrays are also produced, highlighting their potential for biomedical applications. This work establishes a reliable and straightforward route from an extremely simple precursor to high-performance PDC micro/nano devices, showcasing promising prospects for applications in advanced microsystems and lightweight metamaterials.