Confined-Melting-Assisted Synthesis of Bismuth Silicate Glass-Ceramic Nanoparticles: Formation and Optical...

Bismuth-based (nano)materials have been attracting increasing interest due to appealing properties such as high refractive indexes, intrinsic opacity, and structural distortions due to the stereochemistry of 6s² lone pair electrons of Bi³⁺. However, the control over specific phases and strategies able to stabilize uniform bismuth-based (nano)materials is still a challenge. In this study, we employed the ability of bismuth to lower the melting point of silica to introduce a new synthetic approach able to confine the growth of bismuth-oxide-based materials into nanostructures. Combining in situ temperature-dependent synchrotron radiation X-ray powder diffraction (XRPD) with high-resolution transmission electron microscopy (HR-TEM) analyses, we demonstrate the evolution of a confined Bi₂O₃-SiO₂ nanosystem from Bi₂SiO₅ to Bi₄Si₃O₁₂ through a melting process. The silica shell acts as both a nanoreactor and a silicon source for the stabilization of bismuth silicate glass-ceramic nanocrystals keeping the original spherical shape. The exciton peak of Bi₂SiO₅ is measured for the first time allowing the estimation of its real energy gap. Moreover, based on a detailed spectroscopic investigation, we discuss the potential and the limitations of Nd³⁺-activated bismuth silicate systems as ratiometric thermometers. The synthetic strategy introduced here could be further explored to stabilize other bismuth-oxide-based materials, opening the way toward the growth of well-defined glass-ceramic nanoparticles.