  The growing interest in 3D printing of silica glass has spurred substantial
research efforts. Our prior work utilizing a liquid silica resin (LSR)
demonstrated high printing accuracy and resolution. However, the resin's
sensitivity to moisture posed limitations, restricting the printing
environment. On the other hand, polyhedral oligomeric silsesquioxane
(POSS)-based materials offer excellent water stability and sinterless features.
Yet, they suffer from relatively high shrinkage due to the presence of
additional organic monomers. In this study, we present a polymeric
silsesquioxane (PSQ) resin with reduced shrinkage, enhanced moisture stability,
and the retention of sinterless features, providing a promising solution for
achieving high-resolution 3D printing of glass objects. Leveraging the
two-photon polymerization (2PP) method, we realized nanostructures with feature
sizes below 80 nm. Moreover, we demonstrate the tunability of the refractive
index by incorporating zirconium moieties into the resin, facilitating the
fabrication of glass micro-optics with varying refractive indices. Importantly,
the self-welding capability observed between two individual components provides
a flexible approach for producing micro-optics with multiple components, each
possessing distinct refractive indices. This research represents a significant
advancement in the field of advanced glass manufacturing, paving the way for
future applications in micro- and nano-scale glass objects.
