Three‐Dimensional SiCN Ceramic Microstructures via Nano‐Stereolithography of Inorganic Polymer Photoresists

Abstract

We report a newly synthesized inorganic polymer photoresist with a high ceramic yield by the functionalization of polyvinylsilazane (KiON VL20) with 2‐isocyanatoethyl methacrylate via linkage or insertion reaction routes. The chemistry of the synthesis and the pyrolytic conversion as well as the mechanical evaluation were investigated by using various analytical instruments. We show for the first time that this photosensitive resin is a novel precursor for the fabrication of complex 3D SiCN ceramic microstructures with a 210 nm resolution via a two‐photon absorbed crosslinking process and subsequent pyrolysis at 600 °C under a nitrogen atmosphere. Moreover, the dimensional deformation during pyrolysis was significantly reduced by adding silica nanoparticles as a filler. In particular, the ceramic microstructures containing 40 wt % silica nanoparticles exhibited a relatively isotropic shrinkage owing to its sliding free from the substrate during pyrolysis.

Synthesis and properties of UV curable polyvinylsilazane as a precursor for micro‐structuring

“…It is reported that the insertion reaction route of the isocyanate group into the Si-N bond was not feasible due to the steric hindrance of bulky diacrylate groups. 15 At here, we propose the reaction mechanism that diacrylate group was grafted by formation of bridging urea group via the linkage route which is shown in Scheme 1.…”

“…[14] Formerly, we reported the fabrication of a three-dimensional inorganic polymer structure using acrylated PVSZ as an inorganic photoresist. [15][16][17] And also other photosensitive PVSZ with different UV sensitivities was prepared. [18] Throughout the works, we obviously learned that the development of new photoresist with improved photosensitivity is essential for fabricating the nano-/micro-structures with better resolution via photopatterning techniques, mainly due to the faster curing kinetics.…”

Caracterización microscópica de texturas superficiales fabricadas aditivamente mediante estereolitografía láser

“…Recientemente, una serie de impresoras tridimensionales (3D) se han desarrollado y son asequibles tanto para usos industriales como personales [7]. Existen principalmente dos tipos de impresoras 3D, la que utiliza repetidamente un proceso de adición de material con bajo punto de fusión, como en el caso del modelado por deposición fundida (FDM) [8], y la estereolitografía (SLA) [9]- [11] que utiliza resina curable por radiación ultravioleta (UV) [12]- [14]. Algunos de los procesos de estereolitografía han utilizado resina curable por UV con materiales en polvo de cerámica dispersos [15]- [18].…”

Two-photon controlled sol–gel condensation for the microfabrication of silica based microstructures. The role of photoacids and photobases

“…Two-photon polymerized ORMOC-ERS were introduced with structure sizes of 200 nm. 4 Later on, those strategies were extended to Zr-Si based oxide materials, 5 SiCN nanostructures, 6 or TiO 2 patterning. 7,8 In all these examples, the control of the microstructure was performed via twophoton induced polymerization reactions and the polymeric organic network was used as template for the structuration.…”